Two-step deposition process

ABSTRACT

The present invention provides a process for producing a layer of a crystalline material comprising a perovskite or a hexahalometallate, which process comprises: (i) exposing a substrate to a vapour comprising a first precursor compound in a first chamber to produce a layer of the first precursor compound on the substrate; and (ii) exposing the layer of the first precursor compound to a vapour comprising a second precursor compound in a second chamber to produce the layer of a crystalline material, wherein the pressure in the second chamber is above high vacuum. The invention also provides a process for producing a layer of a crystalline material comprising a perovskite or a hexahalometallate, which process comprises exposing a layer of a first precursor compound on a substrate to a vapour comprising a second precursor compound in a chamber to produce the layer of a crystalline material, wherein the pressure in the chamber is greater than high vacuum and less than atmospheric pressure. The invention also provides a process for producing a semiconductor device comprising a layer of a crystalline material, which process comprises producing said layer of a crystalline material by a process as according to the invention.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application represents the national stage entry of PCTInternational Application No. PCT/GB2015/051993 filed Jul. 9, 2015 andclaims priority to Great Britain Patent Application No. 1412201.4 filedon Jul. 9, 2014. The contents of this application are herebyincorporated by reference as if set forth in their entirety herein.

FIELD OF THE INVENTION

The present invention relates to a process for producing a layer of acrystalline material. A process for producing a semiconductor devicecomprising a layer of a crystalline material is also described.

The work leading to this invention has received funding from theEuropean Community's Seventh Framework Programme (FP7/2007-2013) undergrant agreement no. 279881.

BACKGROUND OF THE INVENTION

Hybrid organic-inorganic perovskite materials have recently become atopic of extreme interest for photovoltaics, with devices based on thesematerials now reaching power conversion efficiencies of above 15%. Otherphotoactive crystalline materials are also of substantial currentinterest.

The key to achieving the highest efficiencies with this material appearsto be optimisation of the perovskite or crystalline material filmquality. Typically, perovskite and other crystalline films have beendeposited by spin-coating a precursor containing necessary components toform the perovskite: a metal halide and an organic component. However,spin-coating is by its very nature a process which can easily result innon-uniform films or films with pinholes. Spin-coating is highlysusceptible to microscopic amounts of dust on the substrate,precipitates in the solution, local atmosphere composition andtemperature, and human error when depositing. These factors combine tomake spin-coating an inherently poorly reproducible process forproducing organometal perovskites and other crystalline materials.Moreover, spin-coating is a process which cannot be easily scaled up.

A key breakthrough was achieved by Liu, Snaith et al. (Liu, M.;Johnston, M. B.; Snaith, H. J. Efficient Planar HeterojunctionPerovskite Solar Cells by Vapour Deposition. Nature 2013, 501, 395-398),who describe a high vacuum two-source vapour deposition technique toproduce extremely uniform, high quality perovskite films, resulting inthe most efficient devices at the time. However, this is a costlyprocess; it requires large quantities of the reagents as well as hightemperatures and most importantly, a high vacuum chamber.

Additionally, due to the volatile nature of the organic componentemployed, it is difficult to control the rate of its deposition, makingthis process difficult to reproduce between batches.

A second breakthrough was achieved by Burschka et al. (Burschka, J.;Pellet, N.; Moon, S.-J.; Humphry-Baker, R.; Gao, P.; Nazeeruddin, M. K.;Gräzel, M. Sequential Deposition as a Route to High-PerformancePerovskite-Sensitized Solar Cells. Nature 2013, 499, 316-319) whodescribe a two-step deposition route to form high-quality perovskitefilms using solution-processing. The metal halide component isspin-coated on a meso-structured substrate and the layer of the metalhalide is subsequently dipped in a solution containing the dissolvedorganic component. The perovskite film forms spontaneously. Recentresearch has pointed to planar perovskite heterojunction solar cellshaving the greatest potential to reach the highest efficiencies, ratherthan those based on a meso-structured (e.g. mesoporous) oxide, and hencethe two-step approach was recently adapted for planar solar cells byLiu, Kelly et al. (Liu, D.; Kelly, T. L. Perovskite Solar Cells with aPlanar Heterojunction Structure Prepared Using Room-Temperature SolutionProcessing Techniques. Nat. Photonics 2013, 1-6). This produced some ofthe most efficient perovskite solar cells to date. However, the filmsproduced in this way are substantially non-uniform and the surface ofthe perovskite layer comprises large crystallites of greater than amicron in size. The presence of these crystallites causes high surfaceroughness. This is likely to be an issue in Willis of reproducibility:if an electrode touches a crystallite of the perovskite penetrating thehole-transport layer it can provide a recombination pathway, loweringdevice performance and affecting reproducibility. For the best solarcells, an extremely flat perovskite surface would be optimal, allowingonly a thin layer of hole transporting material to be employed, andhence minimising resistive losses in that layer.

In light of this, the most recent development for making smoothperovskite films was made by Chen, Yang et al. (Chen, Q.; Zhou, H.;Hong, Z.; Luo, S.; Duan, H.-S.; Wang, H.-H.; Liu, Y.; Li, G.; Yang, Y.Planar Heterojunction Perovskite Solar Cells via Vapor Assisted SolutionProcess. J. Am. Chem. Soc. 2013, 3-6), who have modified the two-stepdeposition process, in the planar perovskite solar cell configuration,by replacing the solution-phase organic dipping step with an atmosphericpressure vapour-phase conversion, where the spincoated metal halide isannealed in an atmosphere of the sublimed organic component to convertit to the perovskite. This results in perovskite films of low roughnessand high purity. However, this procedure still makes use of spin-coatingto form the metal halide initial film, which results in theaforementioned issues with reproducibility and non-uniformity.

Kitazawa et al. (Kitazawa, N.; Yaemponga, D.; Aono, M.; Watanabe, Y.Optical Properties of Organicinorganic Hybrid Films Prepared by theTwo-Step Growth Process. J. Lumin. 2009, 129, 1036-1041) describes aprocess to fabricate nanocrystal-sized (C₈H₁₇NH₃)PbBr₄, using two highvacuum stages. A first vacuum evaporation of a metal halide layerfollowed by a second vacuum evaporation of an organic halide. Asequential two-step vacuum deposition process is also described in Hu etal. (H. Hu, D. Wang, Y. Zhou, J. Zhang, S. Lv, S. Pang, X. Chen, Z. Liu,N. P. Padture and G. Cui, RSC Adv., 2014, DOI: 10.1039/C4RA03820G).

Methods which make use of vacuum evaporation to form the metal halidelayer followed by completion of the perovskite by dipping the vacuumevaporated metal halide layer in a solution of the organic componenthave not succeeded in producing high quality films. The use of a secondsolution-based step results in unsuitable perovskite films comprisinglarge crystals and unstable device performance (see Comparative Example2).

Thus, it is an object of the invention to provide an effective processfor the production of perovskite layers. In particular, it is desirableto produce layers of a crystalline material (e.g. perovskite) by aprocess which is readily reproducible, easy to scale up and produceslayers of a crystalline material having a flat surface.

SUMMARY OF THE INVENTION

Here a new approach to prepare extremely smooth, pinhole-free perovskite(and other crystalline material) films of high purity, for use inphotovoltaics and other optical and semiconducting applications ispresented. The technique makes use of a two-stage vapour phase techniqueto ensure extremely high quality of films, with no solution-processingrequired at all. For instance, initially the metal halide can bedeposited via thermal vapour deposition, under high vacuum, to produce ahigh quality, smooth and pinhole-free film. Subsequently, the film isplaced and optionally heated in an atmosphere saturated with thesublimed organic component, causing it to undergo conversion to theperovskite. The advantage of this technique over the previouslydeveloped methods is two-fold. Firstly, no solution-processing isrequired, which enables the most uniform and high quality films to beproduced. Secondly, by carrying out the film fabrication in two stages,and depositing the organic at relatively high pressures and relativelylow temperatures, it is a much more controlled and reproducible methodthan the dual source, high vacuum method of Liu, Snaith et al. Theprocess of the invention allows high efficiency perovskite solar cellsto be fabricated, and furthermore can enable the fabrication of newperovskite or perovskite-like hybrid materials. The process of theinvention circumvents the problems of prior art approaches (for instanceChen et al.) by employing solvent-free vapour deposition approaches.Furthermore, the use of a two-stage vapour process allows materialswhich have poor solubilities to be used. For instance, the processallows the production of new copper based materials.

The invention provides a process for producing a layer of a crystallinematerial that comprises a perovskite or a hexahalometallate, whichprocess comprises:

-   -   (i) exposing a substrate to a vapour comprising a first        precursor compound in a first chamber to produce a layer of the        first precursor compound on the substrate; and    -   (ii) exposing the layer of the first precursor compound to a        vapour comprising a second precursor compound in a second        chamber to produce the layer of a crystalline material, wherein        the pressure in the second chamber is greater than or equal to 1        mbar.

In step (i) the substrate may be exposed to a directional vapourcomprising the first precursor compound. In step (ii) the layer of thefirst precursor compound may be exposed to a non-directional vapourcomprising the second precursor compound. The first chamber and thesecond chamber are preferably different chambers.

The invention also provides a process for producing a layer of acrystalline material that comprises a perovskite or a hexahalometallate,which process comprises:

-   -   (i) exposing a substrate to a vapour comprising a first        precursor compound in a first chamber to produce a layer of the        first precursor compound on the substrate, wherein the first        chamber is under a high vacuum; and    -   (ii) exposing the layer of the first precursor compound to a        vapour comprising a second precursor compound in a second        chamber to produce the layer of a crystalline material, wherein        the second chamber is not under a high vacuum. Preferably, the        pressure in the second chamber is also less than atmospheric        pressure.

In step (i) the substrate may be exposed to a directional vapourcomprising the first precursor compound. In step (ii) the layer of thefirst precursor compound may be exposed to a non-directional vapourcomprising the second precursor compound. The first chamber and thesecond chamber are preferably different chambers.

The pressure in the first chamber may be less than or equal to 10⁻⁴mbar, and preferably the pressure in the first chamber is less than orequal to 10⁻⁵ mbar. The pressure in the second chamber may be not lessthan 10⁻⁴ mbar, and preferably the pressure in the second chamber isgreater than or equal to 1 mbar.

The invention also provides a layer of a crystalline material obtainableby a process according to the invention for producing a layer of acrystalline material.

The invention also provides a process for producing a semiconductordevice comprising a layer of a crystalline material, which processcomprises producing said layer of a crystalline material by a processaccording to the invention for producing a layer of a crystallinematerial. A semiconductor device obtainable by a process according tothe invention is also provided.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows scanning electron microscope images of (A) a top-view of aperovskite film grown by two-step vapour deposition, (B) short and (C)large scale cross-sections of devices incorporating a perovskite filmgrown by two-step vapour deposition.

FIG. 2 shows an XRD pattern comparing evaporated PbI₂ before (peaksmarked with ⁺) and after (peaks marked with *) MAI (methyl ammoniumiodide) vapour treatment. This shows that after treatment all of thePbI₂ is converted into MAPbI₃. Additional peaks (marked with −)originating from the substrate are highlighted in the control spectrum.

FIG. 3 shows current voltages characteristics under simulated AM1.5sunlight (upper curve is light; lower curve is dark) for a devicecomprising a photoactive layer of methylammonium lead triiodide producedby a two-step vapour/vapour deposition.

FIG. 4 shows a schematic diagram of an example of a two-step processaccording to the invention. In step 1 a substrate (A) is exposed to avapour of a first precursor compound (for instance by vacuumdeposition). In step 2 a substrate (A) comprising a layer of the firstprecursor compound is placed in a second chamber (B) together with solidsecond precursor compound (C) and the second chamber is heated (T) toproduce a sublimed vapour of the second precursor compound.

FIG. 5 shows conversion of lead iodide to methylammonium lead triiodidevia a two-stage process, one with spin-coated lead iodide and one withevaporated lead iodide. The Figure shows scanning electron micrographsof a) spin-coated lead iodide surface, b) methylammonium lead triiodidesurface produced by atmospheric vapour phase organic treatment ofspin-coated lead iodide, c) evaporated lead iodide surface, d)methylammonium lead triiodide surface produced by atmospheric vapourphase organic treatment of spin-coated lead iodide.

FIG. 6 shows X-ray diffraction patterns of a film of spin-coated leadiodide undergoing conversion to methylammonium lead triiodide after acertain time in the methylammonium iodide atmosphere. Total conversionis observed after ˜1 h 30 m. Horizontal axes represent 2θ. Vertical axesrepresent arbitrary units.

FIG. 7 shows UV-vis absorbance spectra of the methylammonium leadtriiodide films produced from spin-coated lead iodide after a certaintime in a methylammonium iodide atmosphere (30, 60 or 90 minutes).

FIG. 8 shows photovoltaic devices comprising methylammonium leadtriiodide fabricated via organic vapour conversion of spin-coated andevaporated lead triiodide: a) cross-sectional SEM of device formed fromconverted spin-coated lead iodide; and b) cross-sectional SEM of deviceformed from converted evaporated lead iodide.

FIG. 9 shows current-voltage characteristics of methylammonium leadtriiodide solar cells fabricated via spin-coated PbI₂/vapour depositedMAI: as a planar heterojunction (upper); and on mesoporous TiO₂ (lower).

FIG. 10 shows XRD spectra showing partial conversion of a film ofspin-coated tin iodide into methylammonium tin triiodide, aftertreatment in a methylammonium iodide atmosphere. Perovskite peaks arelabelled with a *.

FIG. 11 shows the XRD of a new copper-based material formed using aspin-coating metal halide/vapour deposited organic method with CuBr₂ andmethylammonium chloride.

FIG. 12 shows the XRD of a copper-based material formed using aspin-coating metal halide/vapour deposited organic method with CuCl₂ andmethylammonium chloride.

FIG. 13 shows the XRD of a copper-based material formed using aspin-coating metal halide/vapour deposited organic method with CuCl₂ andammonium chloride.

FIG. 14 shows UV-Vis absorption of copper-based materials formed fromCuBr₂ and methylammonium chloride and CuCl₂ and methylammonium chlorideusing a spin-coating metal halide/vapour deposited organic method.

FIG. 15 shows SEM images showing the evolution of perovskite crystalgrowth at room temperature by dip coating a PbCl₂ thin-film into a 20mg/ml isopropanol solution of methylammonium iodide after (a) 0 s, (b) 1s, (c) 10 s, (d) 100 s, (e) 1000 s, (f) 10000 s.

FIG. 16 shows normalised XRD spectra for perovskite films at differentdipping times, t.

FIG. 17 shows SEM images showing the evolution of perovskite crystalgrowth at room temperature by dip coating a PbI₂ thin-film into a 20mg/ml isopropanol solution of methylammonium iodide after (a) 0 s, (b) 1s, (c) 10 s, (d) 100 s, (e) 1000 s, (f) 8000 s.

FIG. 18 shows normalised XRD spectra for perovskite films at differentdipping times, t.

FIG. 19 shows morphology variation when forming perovskite from PbCl₂ at90° C. after 500 seconds using the following MAI concentrations: (a) 3mg/ml, (b) 4 mg/ml, (c) 5 mg/ml, (d) 6 mg/ml, (e) 7 mg/ml.

FIG. 20 shows morphology variation when forming perovskite from PbI₂ at90° C. after 500 seconds using the following MAI concentrations: (a) 3mg/ml, (b) 4 mg/ml, (c) 5 mg/ml, (d) 6 mg/ml, (e) 7 mg/ml.

FIG. 21 shows current density-voltage characteristics for the highestefficiency device based on an active layer formed by dip coating of aPbCl₂ film at 90° C. in a solution of 6.5 mg/ml MAI in isopropanol for400s.

FIG. 22 shows a histogram of device efficiencies from 12 devicesfabricated by vapour-solution method.

FIG. 23 shows a histogram of J-V curve stabilities for 12 devicesfabricated by vapour-solution method.

FIG. 24 shows a top-view SEM of the surface of a formamidinium leadtriiodide layer produced by two-step vapour deposition.

FIG. 25 shows a XRD pattern taken of a formamidinium lead triiodidelayer produced by two-step vapour deposition.

FIG. 26 shows the UV-vis absorbance spectra of a formamidinium leadtriiodide layer produced by two-step vapour deposition.

DETAILED DESCRIPTION OF THE INVENTION

Definitions

The term “perovskite”, as used herein, refers to a material with athree-dimensional crystal structure related to that of CaTiO₃ or amaterial comprising a layer of material, which layer has a structurerelated to that of CaTiO₃. The structure of CaTiO₃ can be represented bythe formula ABX₃, wherein A and B are cations of different sizes and Xis an anion. In the unit cell, the A cations are at (0,0,0), the Bcations are at (½, ½, ½) and the X anions are at (½, ½, 0). The A cationis usually larger than the B cation. The skilled person will appreciatethat when A, B and X are varied, the different ion sizes may cause thestructure of the perovskite material to distort away from the structureadopted by CaTiO₃ to a lower-symmetry distorted structure. The symmetrywill also be lower if the material comprises a layer that has astructure related to that of CaTiO₃. Materials comprising a layer ofperovskite material are well known. For instance, the structure ofmaterials adopting the K₂NiF₄-type structure comprises a layer ofperovskite material. The skilled person will appreciate that aperovskite material can be represented by the formula [A][B][X]₃,wherein [A] is at least one cation, [B] is at least one cation and [X]is at least one anion. When the perovskite comprises more than one Acation, the different A cations may distributed over the A sites in anordered or disordered way. When the perovskite comprises more than one Bcation, the different B cations may distributed over the B sites in anordered or disordered way. When the perovskite comprise more than one Xanion, the different X anions may distributed over the X sites in anordered or disordered way. The symmetry of a perovskite comprising morethan one A cation, more than one B cation or more than one X cation,will be lower than that of CaTiO₃.

The term “metal halide perovskite”, as used herein, refers to aperovskite, the formula of which contains at least one metal cation andat least one halide anion. The taint “organometal halide perovskite”, asused herein, refers to a metal halide perovskite, the formula of whichcontains at least one organic cation.

The term “hexahalometallate”, as used herein, refers to a compound whichcomprises an anion of the formula [MX₆]^(n−) wherein M is a metal atom,each X is independently a halide anion and n is an integer from 1 to 4.

The term “chalcogenide” refers to anions of the elements of group 16,for instance O²⁻, S²⁻, Se²⁻, or Te²⁻. Typically, the chalcogenides aretaken to be S²⁻, Se²⁻, and Te²⁻.

The term “monocation”, as used herein, refers to any cation with asingle positive charge, i.e. a cation of formula A⁺ where A is anymoiety, for instance a metal atom or an organic moiety. The term“dication”, as used herein, refers to any cation with a double positivecharge, i.e. a cation of formula A²⁺ where A is any moiety, for instancea metal atom or an organic moiety. The term “tetracation”, as usedherein, refers to any cation with a quadruple positive charge, i.e. acation of formula A⁴⁺ where A is any moiety, for instance a metal atom.

The term “alkyl”, as used herein, refers to a linear or branched chainsaturated hydrocarbon radical. An alkyl group may be a C₁₋₂₀ alkylgroup, a C₁₋₁₄ alkyl group, a C₁₋₁₀ alkyl group, a C₁₋₆ alkyl group or aC₁₋₄ alkyl group. Examples of a C₁₋₁₀ alkyl group are methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl. Examples ofC₁₋₆ alkyl groups are methyl, ethyl, propyl, butyl, pentyl or hexyl.Examples of C₁₋₄ alkyl groups are methyl, ethyl, i-propyl, n-propyl,t-butyl, s-butyl or n-butyl. If the term “alkyl” is used without aprefix specifying the number of carbons anywhere herein, it has from 1to 6 carbons (and this also applies to any other organic group referredto herein).

The term “cycloalkyl”, as used herein, refers to a saturated orpartially unsaturated cyclic hydrocarbon radical. A cycloalkyl group maybe a C₃₋₁₀ cycloalkyl group, a C₃₋₈ cycloalkyl group or a C₃₋₆cycloalkyl group. Examples of a C3-8 cycloalkyl group includecyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl,cyclohex-1,3-dienyl, cycloheptyl and cyclooctyl. Examples of a C₃₋₆cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, andcyclohexyl.

The term “alkenyl”, as used herein, refers to a linear or branched chainhydrocarbon radical comprising one or more double bonds. An alkenylgroup may be a C₂₋₂₀ alkenyl group, a C₂₋₁₄ alkane group, a C₂₋₁₀alkenyl group, a C₂₋₆ alkenyl group or a C₂₋₄ alkenyl group. Examples ofa C₂₋₁₀ alkenyl group are ethenyl (vinyl), propenyl, butenyl, pentenyl,hexenyl, heptenyl, octenyl, nonenyl or decenyl. Examples of C₂₋₆ alkenylgroups are ethenyl, propenyl, butenyl, pentenyl or hexenyl. Examples ofC₂₄ alkenyl groups are ethenyl, propenyl, n-propenyl, s-butenyl orn-butenyl. Alkenyl groups typically comprise one or two double bonds.

The term “alkynyl”, as used herein, refers to a linear or branched chainhydrocarbon radical comprising one or more triple bonds. An alkynylgroup may be a C₂₋₂₀ alkynyl group, a C₂₋₁₄ alkynyl group, a C₂₋₁₀alkynyl group, a C₂₋₆ alkynyl group or a C₂₋₄ alkynyl group. Examples ofa C₂₋₁₀ alkynyl group are ethynyl, propynyl, butynyl, pentynyl, hexynyl,heptynyl, octynyl, nonynyl or decynyl. Examples of C1-6 alkynyl groupsare ethynyl, propynyl, butynyl, pentynyl or hexynyl. Alkynyl groupstypically comprise one or two triple bonds.

The term “aryl”, as used herein, refers to a monocyclic, bicyclic orpolycyclic aromatic ring which contains from 6 to 14 carbon atoms,typically from 6 to 10 carbon atoms, in the ring portion. Examplesinclude phenyl, naphthyl, indenyl, indanyl, anthrecenyl and pyrenylgroups. The term “aryl group”, as used herein, includes heteroarylgroups. The term “heteroaryl”, as used herein, refers to monocyclic orbicyclic heteroaromatic rings which typically contains from six to tenatoms in the ring portion including one or more heteroatoms. Aheteroaryl group is generally a 5- or 6-membered ring, containing atleast one heteroatom selected from O, S, N, P, Se and Si. It maycontain, for example, one, two or three heteroatoms. Examples ofheteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl,fiiranyl, thienyl, pyrazolidinyl, pyrrolyl, oxazolyl, oxadiazolyl,isoxazolyl, thiadiazolyl, thiazolyl, isothiazolyl, imidazolyl,pyrazolyl, quinolyl and isoquinolyl.

The terms “alkylene”, “cycloalkylene”, “alkenylene”, “alkynylene”, and“arylene”, as used herein, refer to bivalent groups obtained by removinga hydrogen atom from an alkyl, cycloalkyl, alkenyl, alkynyl, or arylgroup, respectively. An alkylene group may be a C₁₋₁₈ alkylene group, aC₁₋₁₄ alkylene group, a C₁₋₁₀ alkylene group, a C₁₋₆ alkylene group or aC₁₋₄ alkylene group. Examples of C₁₋₆ alkylene groups are methylene,ethylene, propylene, butylene, pentylene and hexylene. A cycloalkylenegroup may be a C₃₋₁₀ cycloalkylene group, a C₃₋₈ cycloalkylene group ora C₃₋₆ cycloalkylene group. Examples of C₃₋₆ cycloalkylene groupsinclude cyclopentylene and cyclohexylene. An alkenylene group may be aC₂₋₁₈ alkenylene group, a C₂₋₁₄ alkenylene group, a C₂₋₁₀ alkenylenegroup, a C₂₋₆ alkenylene group or a C₂₋₄ alkenylene group. Examples of aC₂₋₄ alkenylene group include ethenylene (vinylene), propenylene andbutenylene. An alkynylene group may be a C₂₋₁₈ alkynylene group, a C₂₋₁₄alkynylene group, a C₂₋₁₀ alkynylene group, a C₂₋₆ alkynylene group or aC₂₋₄ alkynylene group. Examples of a C₂₋₄ alkynylene group includeethynylene and propynylene. Examples of arylene groups include phenyleneand a diradical derived from thiophene. For alkylene, cycloalkylene,alkenylene, alkynylene, and arylene, these groups may be bonded to othergroups at any two positions on the group. Thus, propylene includes—CH₂CH₂CH₂— and —CH₂CH(CH₃)—, and phenylene includes ortho-, meta- andpara-phenylene.

The term “substituted”, as used herein in the context of substitutedorganic groups, refers to an organic group which bears one or moresubstituents selected from C₁₋₁₀ alkyl, aryl (as defined herein), cyano,amino, nitro, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino, arylamino,diarylamino, aryl(C₁₋₁₀)alkylamino, amido, acylamido, hydroxy, oxo,halo, carboxy, ester, acyl, acyloxy, C₁₋₁₀ alkoxy, aryloxy,halo(C₁₋₁₀)alkyl, sulfonic acid, thiol, C₁₋₁₀ alkylthio, arylthio,sulfonyl, phosphoric acid, phosphate ester, phosphonic acid andphosphonate ester. Examples of substituted alkyl groups includehaloalkyl, perhaloalkyl, hydroxyalkyl, aminoalkyl, alkoxyalkyl andalkaryl groups. When a group is substituted, it may bear 1, 2 or 3substituents. For instance, a substituted group may have 1 or 2substitutents.

The term “porous”, as used herein, refers to a material within whichpores are arranged. Thus, for instance, in a porous scaffold materialthe pores are volumes within the scaffold where there is no scaffoldmaterial. The individual pores may be the same size or different sizes.The size of the pores is defined as the “pore size”. The limiting sizeof a pore, for most phenomena in which porous solids are involved, isthat of its smallest dimension which, in the absence of any furtherprecision, is referred to as the width of the pore (i.e. the width of aslit-shaped pore, the diameter of a cylindrical or spherical pore,etc.). To avoid a misleading change in scale when comparing cylindricaland slit-shaped pores, one should use the diameter of a cylindrical pore(rather than its length) as its “pore-width” (J. Rouquerol et al.,“Recommendations for the Characterization of Porous Solids”, Pure &Appl. Chem., Vol. 66, No. 8, pp. 1739-1758, 1994). The followingdistinctions and definitions were adopted in previous IUPAC documents(K. S. W. Sing, et al, Pure and Appl. Chem., vol. 57, n04, pp 603-919,1985; and IUPAC “Manual on Catalyst Characterization”, J. Haber, Pureand Appl. Chem., vol. 63, pp. 1227-1246, 1991): micropores have widths(i.e. pore sizes) smaller than 2 nm; Mesopores have widths (i.e. poresizes) of from 2 nm to 50 nm; and Macropores have widths (i.e. poresizes) of greater than 50 nm. In addition, nanopores may be consideredto have widths (i.e. pore sizes) of less than 1 nm.

Pores in a material may include “closed” pores as well as open pores. Aclosed pore is a pore in a material which is a non-connected cavity,i.e. a pore which is isolated within the material and not connected toany other pore and which cannot therefore be accessed by a fluid (e.g. aliquid, such as a solution) to which the material is exposed. An “openpore” on the other hand, would be accessible by such a fluid. Theconcepts of open and closed porosity are discussed in detail in J.Rouquerol et al., “Recommendations for the Characterization of PorousSolids”, Pure & Appl. Chem., Vol. 66, No. 8, pp. 1739-1758, 1994.

Open porosity, therefore, refers to the fraction of the total volume ofthe porous material in which fluid flow could effectively take place. Ittherefore excludes closed pores. The term “open porosity” isinterchangeable with the terms “connected porosity” and “effectiveporosity”, and in the art is commonly reduced simply to “porosity”.

The term “without open porosity”, as used herein, therefore refers to amaterial with no effective open porosity. Thus, a material without openporosity typically has no macropores and no mesopores. A materialwithout open porosity may comprise micropores and nanopores, however.Such micropores and nanopores are typically too small to have a negativeeffect on a material for which low porosity is desired.

The term “compact layer”, as used herein, refers to a layer withoutmesoporosity or macroporosity. A compact layer may sometimes havemicroporosity or nanoporosity.

The term “semiconductor device”, as used herein, refers to a devicecomprising a functional component which comprises a semiconductormaterial. This term may be understood to be synonymous with the term“semiconducting device”. Examples of semiconductor devices include aphotovoltaic device, a solar cell, a photo detector, a photodiode, aphotosensor, a chromogenic device, a transistor, a light-sensitivetransistor, a phototransistor, a solid state triode, a battery, abattery electrode, a capacitor, a super-capacitor, a light-emittingdevice, or a light-emitting diode. The term “optoelectronic device”, asused herein, refers to devices which source, control or detect light.Light is understood to include any electromagnetic radiation. Examplesof optoelectronic devices include photovoltaic devices, photodiodes(including solar cells), phototransistors, photomultipliers,photoresistors, and light emitting diodes.

The term “consisting essentially of” refers to a composition comprisingthe components of which it consists essentially as well as othercomponents, provided that the other components do not materially affectthe essential characteristics of the composition. Typically, acomposition consisting essentially of certain components will comprisegreater than or equal to 95 wt % of those components or greater than orequal to 99 wt % of those components.

The term “high vacuum”, as used herein, refers to a vacuum regimecharacterised by pressures of between 10⁻⁸ mbar and 10⁻⁴ mbar. Incontrast, the term “medium vacuum” refers to a vacuum regimecharacterised by pressures of between 10⁻⁴ mbar and 0.1 mbar, whilst theterms “low vacuum” and “rough vacuum” refer to a vacuum regimecharacterised by pressures of between 0.1 mbar and 1000 mbar.

The term “atmospheric pressure”, as used herein, refers to the pressuregenerated by the gravitational attraction between the earth and itssurrounding air. Atmospheric pressure at the surface of the earth isapproximately 1000 mbar but varies, for instance, from 950 mbar to 1050mbar.

Process for Producing a Layer of a Crystalline Material

The invention provides a process for producing a layer of a crystallinematerial, which process comprises:

-   -   (i) exposing a substrate to a vapour comprising a first        precursor compound in a first chamber to produce a layer of the        first precursor compound on the substrate; and    -   (ii) exposing the layer of the first precursor compound to a        vapour comprising a second precursor compound in a second        chamber to produce the layer of a crystalline material, wherein        the pressure in the second chamber is greater than or equal to 1        mbar.

The invention also provides a process for producing a layer of acrystalline material that comprises a perovskite or a hexahalometallate,which process comprises:

-   -   (i) exposing a substrate to a vapour comprising a first        precursor compound in a first chamber to produce a layer of the        first precursor compound on the substrate, wherein the first        chamber is under a high vacuum; and    -   (ii) exposing the layer of the first precursor compound to a        vapour comprising a second precursor compound in a second        chamber to produce the layer of a crystalline material, wherein        the second chamber is not under a high vacuum.

In both processes, steps (i) and (ii) are usually performedsequentially. Thus, a layer of the first precursor compound is formed instep (i) and then step (ii) is performed. However, steps (i) and (ii)may overlap. For instance, the deposition of the first precursorcompound may still be ongoing when the deposition of the secondprecursor compound begins. The first or second chamber may be evacuatedbefore or after use to remove the vapour of the precursor compound.Further steps may be performed between steps (i) and (ii). As discussedbelow, the first and second chambers may be the same or differentchambers. Thus, sometimes the first chamber and the second chamber arethe same chamber (i.e. there is one chamber, and it is referred to asthe first chamber during step (i) of the process and then referred to asthe second chamber during part (ii) of the process). Alternatively, thefirst chamber and the second chamber may be different chambers. If thefirst and second chambers are different chambers, then the layer of thefirst precursor compound on the substrate is typically transferred fromfirst chamber to the second chamber between steps (i) and (ii).Typically the first and the second chambers are different chambers. Ifthe first and second chambers are different chambers then the processtypically further comprises a step of transferring the substrate (orallowing the substrate to be transferred) between step (i) and step(ii). In this regard, it is preferable that the first and secondchambers are different chambers as this avoids the need to evacuate andthen re-pressurise the chambers between deposition steps.

In both processes, the second chamber is not under a high vacuum (i.e.the pressure in the second chamber is not less than 10⁻⁴ mbar). Forinstance, the pressure of the second chamber may be greater than orequal to 1 mbar. Preferably, the pressure in the second chamber is alsoless than atmospheric pressure. The pressure in the second chamber maytherefore be less than 1000 mbar. Consequently, the pressure in thesecond chamber is greater than 10⁻⁴ mbar and may be less than 1000 mbar.In this regard, it is preferable that the pressure in the second chamberis above high vacuum and less than atmospheric pressure as this providesfor better control over the deposition rate of the second precursorcompound and therefore improved control over the crystal growth and itsquality. In particular, when step (ii) involves exposing the layer ofthe first precursor compound to a non-directional vapour comprising thesecond precursor compound this control of the pressure in the secondchamber, such that the pressure is above high vacuum and less thanatmospheric pressure, allows for control of the partial pressure of thesecond precursor compound in the non-directional vapour, which willdetermine the deposition rate of the second precursor compound. Thepressure of a chamber may be measured by any suitable means and istypically measured by a pressure gauge attached to the chamber. Thepressure of the second chamber is preferably greater than the pressureof the second chamber (i.e. if the first chamber and the second chamberare the same, single chamber, the pressure of the chamber in step (ii)(i.e. the second chamber) is preferably greater than the pressure of thechamber in step (i) (i.e. the first chamber)).

Crystalline Material

The process of the invention may be used to produce a layer of anysuitable crystalline material. Crystalline materials are those which canadopt one or more crystal structures. Crystalline materials thereforetypically comprise crystals or crystallites having an ordered array ofatoms or molecules.

The layer of a crystalline material is often a crystalline layer of acompound. Thus, the process of the invention is often a process forproducing a crystalline layer of a compound. The compound may be anycompound which can form a crystalline layer.

Often the crystalline material is a semiconducting material. Thecrystalline material (or crystalline layer of a compound) often has aband gap of equal to or less than 4.0 eV. Preferably, the crystallinematerial has a band gap of equal to or less than 3.0 eV. For instance,the crystalline material may have a band gap of from 0.1 eV to 4.0 eV,or from 0.5 eV to 3.5 eV. The crystalline material may have a band gapof from 1.0 eV to 3.0 eV.

The crystalline material may be a photoactive material. The crystallinematerial is typically a photoabsorbent material. The crystallinematerial is preferably capable of absorbing light having a wavelength offrom 300 nm to 2000 nm.

The crystalline material present in the layer produced by the presentinvention typically comprises a compound comprising two or moredifferent types of atoms, ions or molecules. The crystalline materialmay comprise a binary, tertiary or quaternary compound. Binary compoundsare those which comprise two different types of atoms, molecules orions. For instance a binary compound is a compound of formulaA_(a)B_(b), wherein A is an ion, atom or molecule, B is a different ion,atom or molecule and a and b are integers. Ternary compounds are thosewhich comprise three different types of atoms, molecules or ions. Forinstance a ternary compound is a compound of formula A_(a)B_(b)C_(c),wherein A is an ion, atom or molecule, B is a different ion, atom ormolecule, C is another different ion, atom or molecule and a, b and care integers. Quaternary compounds are those which comprise fourdifferent types of atoms, molecules or ions. For instance a quaternarycompound is a compound of formula A_(a)B_(b)C_(c)D_(d), wherein A is anion, atom or molecule, B is a different ion, atom or molecule, C isanother different ion, atom or molecule, D is yet another different ion,atom or molecule and a, b, c and d are integers. a, b, c and d are eachtypically from 1 to 6. In these definitions of binary, ternary andquaternary compounds, the ions may be atomic or molecular ions. Thebonds between these different ions, atoms and molecules may be ionic orcovalent or intermediate between ionic and covalent. Often, two or moreions which are very similar may be considered as the same type of ion.For instance, a ternary compound could comprise a first cation, a secondcation and two or more halide anions, as the halide anions may beconsidered to be the same type of ion.

Typically, the crystalline material comprises greater than 90 wt % of asingle compound.

Preferably, the crystalline material comprises greater than 95 wt % of asingle compound. The single compound may be one of those as describedherein.

Often the crystalline material comprises a ternary compound.

The crystalline material may comprise a compound with a formula whichcomprises one or more first cations, one or more second cations and oneor more anions. Thus, the crystalline material may comprise a compoundhaving a formula (I)[A]_(a)[B]_(b)[C]_(c)  (I)wherein [A] is one or more first cations, [B] is one or more secondcations, [C] is one or more anions, a is an integer from 1 to 6, b is aninteger from 1 to 6, and c is an integer from 1 to 18. a is often aninteger from 1 to 3, b is often an integer from 1 to 3, and c is oftenan integer from 1 to 8.

[A] may be at least one monocation selected from any suitablemonocations. [A] is typically at least one monocation selected from Li⁺,Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺ and monovalent organic cations. Monovalentorganic cations are singly positively charged organic cations, whichmay, for instance, have a molecular weight of no greater than 500 g/mol.For instance, [A] may be a single cation selected from Li⁺, Na⁺, K⁺,Rb⁺, Cs⁺, NH₄ ⁺and monovalent organic cations. [A] is preferably atleast one monocation selected from Rb⁺, Cs⁺, NH₄ ⁺ and monovalentorganic cations. For instance, [A] may be a single monocation selectedfrom Rb⁺, Cs⁺, NH₄ ⁺ and monovalent organic cations. In one embodiment,[A] may be at least one inorganic monocation selected from Li⁺, Na⁺, K⁺,Rb⁺, Cs⁺ and NH₄ ⁺. For instance, [A] may be a single inorganicmonocation selected from Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ and NH₄ ⁺. In anotherembodiment, [A] may be at least one monovalent organic cation. Forinstance, [A] may be a single monovalent organic cation.

When [A] is at least one organic monocation, [A] is typically an organicmonocation comprising an N atom. The N atom typically carries thepositive charge (or part of the positive charge). Preferably, [A] is atleast one monocation selected from K⁺, Rb ⁺, Cs⁺, (NR¹R²R³R⁴)⁺,(R¹R²N═CR³R⁴)⁺, (R¹R²N—C(R⁵)═NR³R⁴)⁺ and (R¹R²N—C(NR⁵R⁶)═NR³R⁴)⁺,wherein each of R¹, R², R³, R⁴, R⁵ and R⁶ is independently H, asubstituted or unsubstituted C₁₋₂₀ alkyl group or a substituted orunsubstituted aryl group. For instance, [A] may be a single monocationselected from K⁺, Rb⁺, Cs⁺, (NR¹R²R³R⁴)+, (R¹R²N═CR³R⁴)+,(R¹R²N—C(R⁵)═NR³R⁴)⁺ and (R¹R²N—C(NR⁵R⁶)═NR³R⁴)⁺, wherein each of R¹,R², R³, R4, R5 and R6 is independently H, a substituted or unsubstitutedC₁₋₂₀ alkyl group or a substituted or unsubstituted aryl group. R¹, R²,R³, R⁴, R⁵ and R⁶ are typically independently H, a substituted orunsubstituted C₁₋₆ alkyl group or a substituted or unsubstituted arylgroup. Preferably R¹, R², R³, R⁴, R⁵ and R⁶ are independently H, or anunsubstituted C₁₋₆ alkyl group. For instance, R¹, R², R³, R⁴, R⁵ and R⁶may independently be H, methyl, ethyl or propyl.

Preferably, [A] is at least one monocation selected from K⁺, Rb⁺, Cs⁺,(R1NH3)⁺, (NR₄ ²)⁺, and (H²N—C(R¹)═NH²)⁺, wherein R¹ is H, a substitutedor unsubstituted C₁₋₂₀ alkyl group or a substituted or unsubstitutedaryl group, and each R² is independently a substituted or unsubstitutedC₁₋₁₀ alkyl group. More preferably, R¹ is H or an unsubstituted C₁₋₆alkyl group and each R² is an unsubstituted C₁₋₆ alkyl group. Forinstance, R¹ may be H, methyl, ethyl or propyl and each R² may bemethyl, ethyl and propyl. All R² may be the same and may be methyl,ethyl and propyl.

Thus, [A] may be at least one monocation selected from K⁺, Rb⁺, Cs⁺, NH₄⁺, (CH₃NH₃)⁺, (CH₃CH₂NH₃)⁺, (CH₃CH₂CH₂NH₃)⁺, (N(CH₃)₄)⁺, (N(CH₂CH₃)₄)⁺,(N(CH₂CH₂CH₃)₄)⁺, (H₂N—C(H)═NH₂)⁺ and (H₂N—C(CH₃)═NH₂)⁺. Preferably [A]is at least one monocation selected from Cs⁺, NH₄ ⁺, (CH₃NH₃)⁺,(CH₃CH₂NH₃)⁺, (N(CH₃)₄)⁺, (H₂N—C(H)═NH₂)⁺ and (H₂N—C(CH₃)═NH₂)⁺.Preferably, [A] is a single type of cation, i.e. the compound is offormula A_(a)[B]_(b)[C]_(c). [A] may be a single monocation selectedfrom K⁺, Rb⁺, Cs⁺, NH₄ ⁺, (CH₃NH₃)⁺, (CH₃CH₂NH₃)⁺, (CH₃CH₂CH₂NH₃)⁺,(N(CH₃)₄)⁺, (N(CH₂CH₃)₄)⁺, (N(CH₂CH₂CH₃)₄)⁺, (H₂N—C(H)═NH₂)⁺ and(H₂N—C(CH₃)═NH₂)⁺.

Preferably, [A] is a single monocation selected from Cs⁺, NH₄ ⁺,(CH₃NH₃)⁺, (CH₃CH₂NH₃)⁺, (N(CH₃)₄)⁺, (N(CH₂CH₃)₄)⁺, (H₂N—C(H)═NH₂)⁺ and(H₂N—C(CH₃)═NH₂)⁺. In one embodiment, A is (CH₃NH₃)⁺. In anotherembodiment, A is (H₂N—C(H)═NH₂)⁺.

Often [B] is one or more metal or metalloid cations. Preferably [B] isone or more metal or metalloid dications or [B] is one or more metal ormetalloid tetracations. Metals include elements of groups 3 to 12 of thePeriodic Table of the Elements and Ga, In, Tl, Sn, Pb, Bi and Po.Metalloids include Si, Ge, As, Sb, and Te. For instance, [B] may be atleast one metal or metalloid cation selected from Ti⁴⁺, V⁴⁺, Mn⁴⁺, Fe⁴⁺,Co⁴⁺, Zr⁴⁺, Nb⁴⁺, Mo⁴⁺, Ru⁴⁺, Rh⁴⁺, Pd⁴⁺, Hf⁴⁺, Ta⁴⁺, W⁴⁺, Re⁴⁺, Os⁴⁺,Ir⁴⁺, Pt⁴⁺, Sn⁴⁺, Pb⁴⁺, Po⁴⁺, Si⁴⁺, Ge⁴⁺, Te⁴⁺, Ca²⁺, Sr²⁺, Cd²⁺, Cu²⁺,Ni²⁺, Mn²⁺, Fe²⁺, Co²⁺, Pd²⁺, Ge²⁺, Sn²⁺, Pb²⁺, Sn²⁺, Yb²⁺ and Eu²⁺.Typically, [B] is at least one metal or metalloid cation selected fromPd⁴⁺, W⁴⁺, Re⁴⁺, Os⁴⁺, Ir⁴⁺, Pt⁴⁺, Sn⁴⁺, Pb⁴⁺, Ge⁴⁺, Te⁴⁺, Sn²⁺, Pb²⁺,Cu²⁺, Ge²⁺ and Ni²⁺. For instance, [B] may be a single metal ormetalloid cation selected from Pd⁴⁺, W⁴⁺, Re⁴⁺, Os⁴⁺, Ir⁴⁺,Pt⁴⁺, Sn⁴⁺,Pb⁴⁺, Ge⁴⁺, Te⁴⁺, Sn²⁺, Pb²⁺, Cu²⁺, Ge²⁺ and Ni²⁺. Typically, [B] is atleast one metal or metalloid cation selected from Sn⁴⁺, Pb⁴⁺, Sn²⁺,Sn⁴⁺, and Cu²⁺.

[C] is typically one or more anions selected from halide anions andchalcogenide anions. [C] may therefore be one or more anions selectedfrom F⁻, Cl⁻, Br⁻, I⁻, O²⁻, Se²⁻, and Te²⁻. Often, [C] is one or moreanions selected from Cl⁻, Br⁻, or I⁻ or [C] is one or more anionsselected from S²⁻, Se²⁻, and Te²⁻.

The crystalline compound may therefore comprise a compound of formula(I)[A]_(a)[B]_(b)[C]_(c)  (I)wherein:

-   -   [A] is one or more cations such as those described herein, for        instance one or more organic monocations;    -   [B] is one or more metal or metalloid cations selected from        Pd⁴⁺, W⁴⁺, Re⁴⁺, Os⁴⁺, Ir⁴⁺, Pt⁴⁺, Sn⁴⁺, Pb⁴⁺, Ge⁴⁺, Te⁴⁺, Sn²⁺,        Pb²⁺, Cu²⁺, Ge²⁺ and Ni²⁺;    -   [C] is one or more anions selected from F⁻, Cl⁻, Br⁻, I⁻, O²⁻,        S²⁻, Se²⁻, and Te²⁻;    -   a is an integer from 1 to 3;    -   b is an integer from 1 to 3; and    -   c is an integer from 1 to 8.

For instance, if [A] is one cation (A), [B] is two cations (B1 and B2),and [C] is one anion (C), the crystalline material comprises a compoundof formula A_(a)(B¹,B²)_(b)C_(c). If [A], [B] or [C] is more than oneion, those ions may be present in any proportion. For instance,A_(a)(B¹,B²)_(b)C_(c) includes all compounds of formula A_(a)B_(by)¹B2_(b(1-y))C_(c) wherein y is between 0 and 1, for instance from 0.05to 0.95. Such materials may be referred to as mixed ion materials.

Typically, the crystalline material comprises a perovskite or ahexahalometallate. Preferably the crystalline material comprises aperovskite. The crystalline material often comprises a metal halideperovskite. The crystalline material often comprises an organometalhalide perovskite.

The crystalline material may comprise a perovskite of formula (II):[A][B][X]₃  (II)wherein:

-   -   [A] is at least one monocation;    -   [B] is at least one metal cation, wherein [B] comprises at least        one of Ca²⁺, Sr²⁺, Cd²⁺, Cu²⁺, Ni²⁺, Mn²⁺, Fe²⁺, Co²⁺, Pd²⁺,        Ge²⁺, Sn²⁺, Pb²⁺, Yb²⁺ and Eu²⁺; and    -   [X] is at least one halide anion.

[A] may comprise at least one organic cation as described herein. Forinstance, [A] may comprise one or more organic cations selected from(NR¹R²R³R⁴)⁺, (R¹R²N═CR³R⁴)⁺, (R¹R²N—C(R⁵)═NR³R⁴)⁺ and(R¹R²N—C(NR⁵R⁶)═NR³R⁴)⁺, wherein each of R¹, R², R³, R⁴, R⁵ and R⁶ isindependently H, a substituted or unsubstituted C₁₋₂₀ alkyl group or asubstituted or unsubstituted aryl group. R¹, R², R³, R⁴, R⁵ and R⁶ maybe independently H, or an unsubstituted C₁₋₆ alkyl group. [A] maycomprise one or more organic cations selected from (CH₃NH₃)⁺,(CH₃CH₂NH₃)⁺, (CH₃CH₂CH₂NH₃)⁺, (N(CH₃)₄)⁺, (H₂N—C(H)═NH₂)⁺ and(H₂N—C(CH₃)═NH₂)⁺. [A] may be a single cation selected from (CH₃NH₃)⁺,(CH₃CH₂NH₃)⁺, (CH₃CH₂CH₂NH₃)⁺, (N(CH₃)₄)⁺, (H₂N—C(H)═NH₂)⁺ and(H₂N—C(CH₃)═NH₂)⁺. A is often (CH₃NH₃)⁺, (CH₃CH₂NH₃)⁺ or(CH₃CH₂CH₂NH₃)⁺.

[A] may comprise at least one inorganic cation. For instance, [A] maycomprise one or more inorganic cations selected from Cs⁺, Rb⁺, Cu⁺, Pd⁺,Pt⁺, Ag⁺, Au⁺, Rh⁺, and Ru⁺. [A] may comprise an inorganic cationselected from Cs⁺ and Rb⁺. Typically, [A] comprises one or more cationsselected from (CH₃NH₃)⁺, (H₂N—C(H)═NH₂)⁺ and Cs⁺.

The crystalline material may comprise a perovskite of formula (II):[A][B][X]₃  (II)wherein:

-   -   [A] is at least one organic cation;    -   [B] is at least one metal cation, wherein [B] comprises at least        one of Ca²⁺, Sr²⁺Cd²⁺, Cu²⁺, Ni²⁺, Mn²⁺, Fe²⁺, Co²⁺, Pd²⁺, Ge²⁺,        Sn²⁺, Pb²⁺, Yb²⁺ and Eu²⁺; and    -   [X] is at least one halide anion.

Perovskite materials which may be formed by the process according to theinvention are methylammonium lead iodide, methylammonium lead iodidechloride, methylammonium tin iodide, methylammonium tin iodide chloride,methylammonium lead bromide, formamidinium lead iodide, methylammoniumcopper bromide chloride, methylammonium copper chloride and ammoniumcopper bromide chloride.

The process of the invention allows layers of crystalline materials tobe formed from low solubility precursor compounds, for instance copperprecursor compounds. Thus, in one embodiment, the invention provides aperovskite comprising copper as described herein. The invention mayprovide a compound of formula ACuI₃, ACuBr₃, ACuCl₃, ACuF₃, ACuBrI₂,ACuBr_(x)I_(3-x), ACuBr_(x)Cl_(3-x), ACuF_(3-x)Br_(x), ACuI_(x)Br_(3-x),ACuICl_(3-x), ACuF_(3-x)I_(x), ACuCl_(x)Br_(3-x), ACuI_(3-x)Cl_(x), orACuF_(3-x)Cl_(x) where x is from 0 to 3, and wherein A is a monocationas described herein. For instance, the invention may provide aperovskite which is CH₃NH₃CuI₃, CH₃NH₃CuBr₃, CH₃NH₃CuCl₃, CH₃NH₃CuF₃,CH₃NH₃CuBrI₂, CH3NH3CuBr_(x)I_(3-x), CH₃NH₃CuBr_(x)Cl_(3-x),CH₃NH₃CuF_(3-x)Br_(x), CH₃NH₃CuI_(x)Br3-x, CH₃NH₃CuI_(x)Cl_(3-x),CH₃NH₃CuF_(3-x)I_(x), CH₃NH₃CuCl_(x)Br_(3-x), CH₃NH₃CuI_(3-x)Cl_(x), andCH₃NH₃CuF_(3-x)Cl_(x) where x is from 0 to 3. x may be from 0.05 to2.95.

In one embodiment, the perovskite is a perovskite compound of theformula (IIA):AB[X]₃  (IIA)wherein: A is a monocation; B is a metal cation; and [X] is two or moredifferent halide anions. Preferably, [X] is two or three differenthalide anions. More preferably, [X] is two different halide anions. Themonocation and metal cation may be as defined above. For instance, A maybe an organic cation.

The crystalline material may, for instance, be a perovskite compound offormula (IIC):ABX_(3-x)X′_(x)  (IIC)wherein: A is a monocation; B is a metal cation; X is a first halideanion; X′ is a second halide anion which is different from the firsthalide anion; and x is from 0 to 3. Usually, x is from 0.05 to 0.95. Forinstance, x may be from 0.5 to 2.5, or from 0.75 to 2.25. Typically, xis from 1 to 2. A may be an organic cation.

Again, in formula (IIC), the monocations and metal cations may be asfurther defined hereinbefore. Thus the monocations may be selected fromany organic cation or inorganic cation described above. The metalcations may be selected from divalent metal cations. For instance, themetal cations may be selected from Ca²⁺, Sr²⁺, Cd²⁺, Cu²⁺, Ni²⁺, Mn²⁺,Fe²⁺, Co²⁺, Pd²⁺, Ge²⁺, Sn²⁺, Pb²⁺, Yb²⁺ and Eu²⁺. The metal cation maybe selected from Sn²⁺, Pb²⁺, Cu²⁺, Ge²⁺ and Ni²⁺. Preferably, the metalcation is Sn²⁺, Pb²⁺ or Cu²⁺.

The crystalline material may comprise, or consist essentially of, aperovskite compound selected from APbI₃, APbBr₃, APbCl₃, APbF₃,APbBr_(x)I_(3-x), APbBr_(x)Cl_(3-x), APbI_(x)Br_(3-x), APbI_(x)Cl_(3-x),APbCl_(x)Br_(3-x), APbI_(3-x)Cl_(x), ASnI₃, ASnBr₃, ASnCl₃, ASnF₃,ASnBrI₂, ASnBrxI_(3-x), ASnBr_(x)Cl_(3-x), ASnF_(3-x)Br_(3-x),ASnI_(x)Br_(3-x), ASnI_(x)Cl_(3-x), ASnF_(3-x)I_(x), ASnCl_(x)Br_(3-x),ASnI_(3-x)Cl_(x) and ASnF_(3-x)Cl_(x), ACuI₃, ACuBr₃, ACuCl₃, ACuF₃,ACuBrI₂, ACuBr_(x)I_(3-x), ACuBr_(x)Cl_(3-x), ACuF_(3-x)Br_(x),ACuI_(x)Br_(3-x), ACuI_(x)Cl_(3-x), ACuF_(3-x)I_(x), ACuCl_(x)Br_(3-x),ACuI_(3-x)Cl_(x), and ACuF_(3-x)Cl_(x) where x is from 0 to 3, andwherein A is a monocation as described herein or an ammonium cation. xmay be from 0.05 to 2.96. For instance, x may be from 0.1 to 2.9, orfrom 0.5 to 2.5. In some cases, x is from 0.75 to 2.25, or from 1 to 2.A may be an organic cation.

The crystalline material may comprise, or consist essentially of, aperovskite compound selected from CH₃NH₃PbI₃, CH₃NH₃PbBr₃, CH₃NH₃PbCl₃,CH₃NH₃PbF₃, CH₃NH₃PbBr_(x)I_(3-x), CH₃NH₃PbBr_(x)Cl_(3-x),CH₃NH₃PbI_(x)Br_(3-x), CH₃NH₃PbI_(x)Cl_(3-x), CH₃NH₃PbCl_(x)Br_(3-x),CH₃NH₃PbI_(3-x)Cl_(x), CH₃NH₃SnI₃, CH₃NH₃SnBr₃, CH₃NH₃SnCl₃, CH₃NH₃SnF₃,CH₃NH₃SnBrI₂, CH₃NH₃SnBr_(x)I_(3-x), CH₃NH₃SnBr_(3-x)Cl_(3-x),CH₃NH₃SnF_(3-x)Br_(x), CH₃NH₃SnI_(x)Br_(3-x), CH₃NH₃SnI_(x)Cl_(3-x),CH₃NH₃SnF_(3-x)I_(x), CH₃NH₃SnCl_(x)Br_(3-x), CH₃NH₃SnI_(3-x)Cl_(x), andCH₃NH₃SnF_(3-x)Cl_(x), CH₃NH₃CuI₃, CH₃NH₃CuBr₃, CH₃NH₃CuCl₃, CH₃NH₃CuF₃,CH₃NH₃CuBrI₂, CH3NH3CuBr_(x)I_(3-x), CH₃NH₃CuBr_(x)Cl_(3-x),CH₃NH₃CuF_(3-x)Br_(x), CH₃NH₃CuI_(x)Br_(3-x), CH₃NH₃CuI_(x)Cl_(3-x),CH₃NH₃CuF_(3-x)I_(x), CH₃NH₃CuCl_(x)Br_(3-x), CH₃NH₃CuI_(3-x)Cl_(x), andCH₃NH₃CuF_(3-x)Cl_(x) where x is from 0 to 3. x may be from 0.05 to2.95. For instance, x may be from 0.1 to 2.9, or from 0.5 to 2.5. Insome cases, x is from 0.75 to 2.25, or from 1 to 2.

The crystalline material may comprise, or consist essentially of, aperovskite compound selected from CH₃NH₃PbI₃, CH₃NH₃PbBr₃, CH₃NH₃PbCl₃,CH₃NH₃PbF₃, CH₃NH₃PbBrI₂, CH₃NH₃PbCl₂, CH₃NH₃PbIBr₂, CH₃NH₃PbICl₂,CH₃NH₃PbClBr₂, CH₃NH₃PbI₂Cl, CH₃NH₃SnI₃, CH₃NH₃SnBr₃, CH₃NH₃SnCl₃,CH₃NH₃SnF₃, CH₃NH₃SnBrI₂, CH₃NH₃SnBrCl₂, CH₃NH₃SnF₂Br, CH₃NH₃SnIBr₂,CH₃NH₃SnICl₂, CH₃NH₃SnF₂I, CH₃NH₃SnClBr₂, CH₃NH₃SnI₂Cl, andCH₃NH₃SnF₂Cl.

The crystalline material may comprise, or consist essentially of, aperovskite compound selected from CH₃NH₃PbBr_(x)I_(3-x),CH₃NH₃PbBr_(x)Cl_(3-x), CH₃NH₃PbI_(x)Br_(3-x), CH₃NH₃PbI_(x)Cl_(3-x),CH₃NH₃PbCl_(x)Br_(3-x), CH₃NH₃PbI_(3-x)Cl_(x), CH₃NH₃SnBr_(x)I_(3-x),CH₃NH₃SnBr_(x)Cl_(3-x), CH₃NH₃SnF_(3-x) Br_(x), CH₃NH₃SnI_(x)Br_(3-x),CH₃NH₃SnI_(x)Cl_(3-x), CH₃NH₃SnF_(3-x)I_(x), CH₃NH₃SnCl_(x)Br_(3-x),CH₃NH₃SnI_(3-x)Cl_(x), and CH₃NH₃SnF_(3-x)Cl_(x), where x is from 0.05to 2.95. For instance, x may be from 0.5 to 2.5, from 0.75 to 2.25, orfrom 1 to 2.

The perovskite compound may be selected from CH₃NH₃PbBrI₂,CH₃NH₃PbBrCl₂, CH₃NH₃PbIBr₂, CH₃NH₃PbICl₂, CH3NH₃SnF₂Br, andCH₃NH₃SnF₂I. The perovskite may be CH₃NH₃PbCl₂I.

Preferably, the crystalline material comprises, or consists essentiallyof, a perovskite compound selected from CH₃NH₃PbI₃, CH₃NH₃PbBr₃,CH₃NH₃PbCl₃, CH₃NH₃SnI₃, CH₃NH₃SnBr₃, CH₃NH₃SnCl₃, CH₃NH₃CuI₃,CH₃NH₃CuBr₃, CH₃NH₃CuCl₃, NH₄CuI₃, NH₄CuBr₃, NH₄CuCl₃, NH₄CuI₂Br,NH₄CuI₂Cl, NH₄CuBr₂Cl, NH₄CuCl₂Br, CH₃NH₃CuI₂Br, CH₃NH₃CuI₂Cl,CH₃NH₃CuBr₂Cl, and CH₃NH₃CuCl₂Br. More preferably, the crystallinematerial comprises, or consist essentially of, a perovskite compoundselected from CH₃NH₃PbI₃, CH₃NH₃SnI₃, NH₄CuCl₂Br, CH₃NH₃CuCl₃, andCH₃NH₃CuCl₂Br.

The crystalline material may for instance comprise, or consistessentially of, a perovskite compound selected from (H₂N—C(H)═NH₂)PbI₃,(H₂N—C(H)═NH₂)PbBr₃, (H₂N—C(H)═NH₂)PbCl₃, (H₂N—C(H)═NH₂)SnI₃,(H₂N—C(H)═NH₂)SnBr₃, (H₂N—C(H)═NH₂)SnCl₃, (H₂N—C(H)═NH₂)CuI₃,(H₂N—C(H)═NH₂)CuBr₃ and (H₂N—C(H)═NH₂)CuCl₃.

The crystalline material may comprise a hexahalometallate of formula(III):[A]₂[M][X]₆  (III)wherein:

-   -   [A] is at least one monocation;    -   [M] is at least one metal or metalloid tetracation; and    -   [X] is at least one halide anion.

[A] is at least one monocation; [M] is at least one metal or metalloidtetracation; and X is at least one halide anion. In a mixed monocationhexahalometallate, [A] is at least two monocations; [M] is at least onemetal or metalloid tetracation (and typically [M] is a single metal ormetalloid tetracation); and [X] is at least one halide anion (andtypically [X] is a single halide anion). In a mixed metalhexahalometallate, [A] is at least one monocation (and typically [A] isa single monocation); [M] is at least two metal or metalloidtetracations (for instance Ge⁴⁺ and Se⁴⁺); and [X] is at least onehalide anion (and typically [X] is a single halide anion). In a mixedhalide hexahalometallate, [A] is at least one monocation (and typically[A] is a single monocation); [M] is at least one metal or metalloidtetracation (and typically [M] is a single metal tetra cation); and [X]is at least two halide anions, for instance Br⁻ and Cl⁻.

[A] may be at least one monocation selected from any suitablemonocations, such as those described above for a organometal halideperovskite. [A] is typically at least one monocation selected from Li⁺,Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺ and monovalent organic cations. Monovalentorganic cations are singly positively charged organic cations, whichmay, for instance, have a molecular weight of no greater than 500 g/mol.For instance, [A] may be a single cation selected from Li⁺, Na⁺, K⁺,Rb⁺, Cs⁺, NH₄ ⁺ and monovalent organic cations. [A] is preferably atleast one monocation selected from Rb⁺, Cs⁺, NH₄ ⁺ and monovalentorganic cations. For instance, [A] may be a single monocation selectedfrom Rb⁺, Cs⁺, NH₄ ⁺ and monovalent organic cations. In one embodiment,[A] may be at least one inorganic monocation selected from Li⁺, Na⁺, K⁺,Rb⁺, Cs⁺ and NH₄ ⁺. For instance, [A] may be a single inorganicmonocation selected from Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ and NH₄ ⁺. In anotherembodiment, [A] may be at least one monovalent organic cation. Forinstance, [A] may be a single monovalent organic cation.

When [A] is at least one organic monocation, [A] is typically an organicmonocation comprising an N atom. The N atom typically carries thepositive charge (or part of the positive charge). Preferably, [A] is atleast one monocation selected from K⁺, Rb⁺, Cs⁺, (NR¹R²R³R⁴)⁺,(R¹R²N═CR³R⁴)⁺, (R¹R²N—C(R⁵)═NR³R⁴)⁺ and (R¹R²N—C(NR⁵R⁶)═NR³R⁴)⁺,wherein each of R¹, R², R³, R⁴, R⁵ and R⁶ is independently H, asubstituted or unsubstituted C₁₋₂₀ alkyl group or a substituted orunsubstituted aryl group. For instance, [A] may be a single monocationselected from K⁺, Rb⁺, Cs⁺, (NR¹R²R³R⁴)⁺, (R¹R²N═CR³R⁴)⁺,(R¹R²N—C(R⁵)═NR³R⁴)⁺ and (R¹R²N—C(NR⁵R⁶)═NR³R⁴)⁺, wherein each of R¹,R², R³, R⁴, R⁵ and R⁶ is independently H, a substituted or unsubstitutedC₁₋₂₀ alkyl group or a substituted or unsubstituted aryl group. R¹, R²,R³, R⁴, R⁵ and R⁶ are typically independently H, a substituted orunsubstituted C₁₋₆ alkyl group or a substituted or unsubstituted arylgroup. Preferably R¹, R², R³, R⁴, R⁵ and R⁶ are independently H, or anunsubstituted C₁₋₆ alkyl group. For instance, R¹, R², R³, R⁴, R⁵ and R⁶may independently be H, methyl, ethyl or propyl.

Preferably, [A] is at least one monocation selected from K⁺, Rb⁺, Cs⁺,(R¹NH₃)⁺, (NR² ₄)⁺, and (H₂N—C(R¹)═NH₂)⁺, wherein R¹ is H, a substitutedor unsubstituted C₁₋₂₀ alkyl group or a substituted or unsubstitutedaryl group, and each R² is independently a substituted or unsubstitutedC₁₋₁₀ alkyl group. More preferably, R¹ is H or an unsubstituted C₁₋₆alkyl group and each R² is an unsubstituted C₁₋₆ alkyl group. Forinstance, R¹ may be H, methyl, ethyl or propyl and each R² may bemethyl, ethyl and propyl. All R² may be the same and may be methyl,ethyl and propyl.

Thus, [A] may be at least one monocation selected from K⁺, Rb⁺, Cs⁺, NH₄⁺, (CH₃NH₃)⁺, (CH₃CH₂NH₃)⁺, (CH₃CH₂CH₂NH₃)⁺, (N(CH₃)₄)⁺, (N(CH₂CH₃)₄)⁺,(N(CH₂CH₂CH₃)₄)⁺, (H₂N—C(H)═NH₂)⁺ and (H₂N—C(CH₃)═NH₂)⁺. Preferably [A]is at least one monocation selected from Cs⁺, NH₄ ^(+, (CH) ₃NH₃)⁺,(CH₃CH₂NH₃)⁺, (N(CH₃)₄)⁺, (H₂N—C(H)═NH₂)⁺ and (H₂N—C(CH₃)═NH₂)⁺.

Preferably, [A] is a single type of cation, i.e. the hexahalometallateis a compound of formula A₂[M][X]₆. [A] may be a single monocationselected from K⁺, Rb⁺, Cs⁺, NH₄ ⁺, (CH₃NH₃)⁺, (CH₃CH₂NH₃)^(+, (CH)₃CH₂CH₂NH₃)⁺, (N(CH₃)₄)⁺, (N(CH₂CH₃)₄)⁺, (N(CH₂CH₂CH₃)₄)⁺,(H₂N—C(H)═NH₂)⁺ and (H₂N—C(CH₃)═NH₂)⁺. Preferably, [A] is a singlemonocation selected from Cs⁺, NH₄ ⁺, (CH₃NH₃)⁺, (CH₃CH₂NH₃)⁺,(N(CH₃)₄)⁺, (N(CH₂CH₃)₄)⁺, (H₂N—C(H)═NH₂)⁺ and (H₂N—C(CH₃)═NH₂)⁺. In oneembodiment, [A] is (CH₃NH₃)⁺. In another embodiment, [A] is(H₂N—C(H)═NH₂)⁺.

[M] may be any suitable metal or metalloid tetracation. Metals includeelements of groups 3 to 12 of the Periodic Table of the Elements and Ga,In, Tl, Sn, Pb, Bi and Po. Metalloids include Si, Ge, As, Sb, and Te.For instance, [M] may be at least one metal or metalloid tetracationselected from Ti⁴⁺, V⁴⁺, Mn⁴⁺, Fe⁴⁺, Co⁴⁺, Zr⁴⁺, Nb⁴⁺, Mo⁴⁺, Ru⁴⁺, Rh⁴⁺,Pd⁴⁺, Hf⁴⁺, Ta⁴⁺, W⁴⁺, Re⁴⁺, Os⁴⁺, Ir⁴⁺, Pt⁴⁺, Sn⁴⁺, Pb⁴⁺, Po⁴⁺, Si⁴⁺,Ge⁴⁺, and Te⁴⁺. Typically, [M] is at least one metal or metalloidtetracation selected from Pd⁴⁺, W⁴⁺, Re⁴⁺, Os⁴⁺, Ir⁴⁺, Pt⁴⁺, Sn⁴⁺, Pb⁴⁺,Ge⁴⁺, and Te⁴⁺. For instance, [M] may be a single metal or metalloidtetracation selected from Pd⁴⁺, W⁴⁺, Re⁴⁺, Os⁴⁺, Ir⁴⁺, Pt⁴⁺, Sn⁴⁺, Pb⁴⁺,Ge⁴⁺, and Te⁴⁺.

Typically, [M] is at least one metal or metalloid tetracation selectedfrom Sn⁴⁺, Te⁴⁺, Ge⁴⁺, and Re⁴⁺. In one embodiment [M] is at least onemetal or metalloid tetracation selected from Pb⁴⁺, Sn⁴⁺, Te⁴⁺, Ge⁴⁺ andRe⁴⁺. For instance, [M] may be at least one metal or metalloidtetracation selected from Pb⁴⁺, Sn⁴⁺, Te⁴⁺ and Ge⁴⁺. Preferably, [M] isat least one metal or metalloid tetracation selected from Sn⁴⁺, Te⁺, andGe⁴⁺. As discussed above, the hexahalometallate compound may be amixed-metal or a single-metal hexahalometallate. Preferably, thehexahalometallate compound is a single-metal hexahalometallate compound.More preferably, [M] is a single metal or metalloid tetracation selectedfrom Sn⁴⁺, Te⁴⁺, and Ge⁴⁺. For instance, [M] may be a single metal ormetalloid tetracation which is Te⁴⁺. For instance, [M] may be a singlemetal or metalloid tetracation which is Ge⁴⁺. Most preferably, [M] is asingle metal or metalloid tetracation which is Sn⁴⁺.

[X] is at least one halide anion. [X] is therefore at least one halideanion selected from F⁻, Cl⁻, Br⁻ and I⁻. Typically, [X] is at least onehalide anion selected from Cl⁻, Br⁻ and I⁻. The hexahalometallatecompound may be a mixed-halide hexahalometallate or a single-halidehexahalometallate. If the hexahalometallate is mixed, [X] is two, threeor four halide anions selected from F⁻, Cl⁻, Br⁻ and I⁻. Typically, in amixed-halide compound, [X] is two halide anions selected from F⁻, Cl⁻,Br⁻ and I⁻.

Typically, [A] is a single monocation and [M] is a single metal ormetalloid tetracation. Thus, the crystalline material may, for instance,comprise a hexahalometallate compound of formula (IIIA)A₂M[X]₆  (IIIA)wherein: A is a monocation; M is a metal or metalloid tetracation; and[X] is at least one halide anion. [X] may be one, two or three halideanions selected from F⁻, Cl⁻, Br⁻ and I⁻, and preferably selected fromCl⁻, Br⁻ and I⁻. In formula (IIIA), [X] is preferably one or two halideanions selected from Cl⁻, Br⁻ and I⁻.

The crystalline material may, for instance, comprise a hexahalometallatecompound of formula (IIIB)A₂MX_(6-y)X′_(y)  (IIIB)wherein: A is a monocation; M is a metal or metalloid tetracation; X andX′ are each independently a (different) halide anion; and y is from 0 to6. When y is 0 or 6, the hexahalometallate compound is a single-halidecompound. When y is from 0.01 to 5.99 the compound is a mixed-halidehexahalometallate compound. When the compound is a mixed-halidecompound, y may be from 0.05 to 5.95. For instance, y may be from 1.00to 5.00.

The hexahalometallate compound may, for instance, be A₂SnF_(6-y)Cl_(y),A₂SnF_(6-y)Br_(y), A₂SnF_(6-y)I_(y), A₂SnCl_(6-y)Br_(y),A₂SnCl_(6-y)I_(y), A₂SnBr_(6-y)I_(y), A₂TeF_(6-y)Cl_(y),A₂TeF_(6-y)Br_(y), A₂TeF_(6-y)I_(y), A₂TeCl_(6-y)Br_(y),A₂TeCl_(6-y)I_(y), A₂TeBr_(6-y)I_(y), A₂GeF_(6-y)Cl_(y),A₂GeF_(6-y)Br_(y), A₂GeF_(6-y)I_(y), A₂GeCl₆/Br_(y), A₂GeCl_(6-y)I_(y),A₂GeBr_(6-y)I_(y), A₂ReF_(6-y)Cl_(y), A₂ReF_(6-y)Br_(y),A₂ReF_(6-y)I_(y), A₂ReCl_(6-y)Br_(y), A₂ReCl_(6-y)I_(y) orA₂ReBr_(6-y)I_(y), wherein: A is K⁺, Rb⁺, Cs⁺, (R¹NH₃)⁺, (NR² ₄)⁺, or(H₂N—C(R¹)═NH₂)⁺, wherein R¹ is H, a substituted or unsubstituted C₁₋₂₀alkyl group or a substituted or unsubstituted aryl group, and R² is asubstituted or unsubstituted C₁₋₁₀ alkyl group; and y is from 0 to 6.Optionally, y is from 0.01 to 5.99. If the hexahalometallate compound isa mixed-halide compound, y is typically from 1.00 to 5.00. A may be asdefined above. For instance, A may be Cs⁺, NH₄ ⁺, (CH₃NH₃)⁺,(CH₃CH₂NH₃)⁺, (N(CH₃)₄)⁺, (N(CH₂CH₃)₄)⁺, (H₂N—C(H)═NH₂)⁺ or(H₂N—C(CH₃)═NH₂)⁺, for instance Cs⁺, NH₄ ⁺, or (CH₃NH₃)⁺.

The hexahalometallate compound may typically be A₂SnF_(6-y)Cl_(y),A₂SnF_(6-y)Br_(y), A₂SnF_(6-y)I_(y), A₂SnCl_(6-y)Br_(y),A₂SnCl_(6-y)I_(y), or A₂SnBr_(6-y)I_(y), wherein: A is K⁺, Rb⁺, Cs⁺,(R¹NH₃)⁺, (NR² ₄)⁺, or (H₂N—C(R¹)═NH₂)⁺, or A is as defined herein,wherein R¹ is H, a substituted or unsubstituted C₁₋₂₀ alkyl group or asubstituted or unsubstituted aryl group, or R¹ is as defined herein, andR² is a substituted or unsubstituted C₁₋₁₀ alkyl group, or R² is asdefined herein; and y is from 0 to 6 or y is as defined herein.

In another embodiment, the hexahalometallate compound isA₂GeF_(6-y)Cl_(y), A₂GeF_(6-y)Br_(y), A₂GeF_(6-y)I_(y),A₂GeCl_(6-y)Br_(y), A₂GeCl_(6-y)I_(y), or A₂GeBr_(6-y)I_(y), wherein: Ais K⁺, Rb⁺, Cs⁺, (R¹NH₃)⁺, (NR² ₄)⁺, or (H₂N—C(R¹)═NH₂)⁺, or A is asdefined herein, wherein R¹ is H, a substituted or unsubstituted C₁₋₂₀alkyl group or a substituted or unsubstituted aryl group, or R¹ is asdefined herein, and R² is a substituted or unsubstituted C₁₋₁₀ alkylgroup, or R² is as defined herein; and y is from 0 to 6 or y is asdefined herein.

The hexahalometallate compound may, for instance, be A₂TeF_(6-y)Cl_(y),A₂TeF_(6-y)Br_(y), A₂TeF_(6-y)I_(y), A₂TeCl_(6-y)Br_(y),A₂TeCl_(6-y)I_(y), or A₂TeBr_(6-y)I_(y), wherein: A is K⁺, Rb⁺, Cs⁺,(R¹NH₃)⁺, (NR² ₄)⁺, or (H₂N—C(R¹)═NH₂)⁺, or A is as defined herein,wherein R¹ is H, a substituted or unsubstituted C₁₋₂₀ alkyl group or asubstituted or unsubstituted aryl group, or R¹ is as defined herein, andR² is a substituted or unsubstituted C₁₋₁₀ alkyl group, or R² is asdefined herein; and y is from 0 to 6 or y is as defined herein.

Often, y will be from 1.50 to 2.50. For instance, y may be from 1.80 to2.20. This may occur if the compound is produced using two equivalentsof AX′ and one equivalent of MX₄, as discussed below.

In some embodiments, all of the ions are single anions. Thus, thecrystalline material may comprise a hexahalometallate compound offormula (IV)A₂MX₆  (IV)wherein: A is a monocation; M is a metal or metalloid tetracation; and Xis a halide anion. A, M and X may be as defined herein.

The hexahalometallate compound may be A₂SnF₆, A₂SnCl₆, A₂SnBr₆, A₂SnI₆,A₂TeF₆, A₂TeCl₆, A₂TeBr₆, A₂TeI₆, A₂GeF₆, A₂GeCl₆, A₂GeBr₆, A₂GeI₆,A₂ReF₆, A₂ReCl₆, A₂ReBr₆ or A₂ReI₆, wherein: A is K⁺, Rb⁺, Cs⁺,(R¹NH₃)⁺, (NR² ₄)⁺, or (H₂N—C(R¹)═NH₂)⁺, wherein R¹ is H, a substitutedor unsubstituted C₁₋₂₀ alkyl group or a substituted or unsubstitutedaryl group, and R² is a substituted or unsubstituted C₁₋₁₀ alkyl group.A may be as defined herein.

Preferably, the hexahalometallate compound is A₂SnI₆, A₂SnBr₆,A₂SnBr_(6-y)I_(y), A₂SnCl_(6-y)I_(y), or A₂SnCl_(6-y)Br_(y) wherein: Ais K⁺, Rb⁺, Cs⁺, (R¹NH₃)⁺, (NR² ₄)⁺, or (H₂N—C(R¹)═NH₂)⁺, wherein R¹ isH, a substituted or unsubstituted C₁₋₂₀ alkyl group or a substituted orunsubstituted aryl group, and R² is a substituted or unsubstituted C₁₋₁₀alkyl group; and y is from 0.01 to 5.99. A and y may be as definedherein.

More preferably, the hexahalometallate compound is Cs₂SnI₆, Cs₂SnBr₆,Cs₂SnBr_(6-y)I_(y), CS₂SnCl_(6-y)I_(y), Cs₂SnCl_(6-y)Br_(y),(CH₃NH₃)₂SnI₆, (CH₃NH₃)₂SnBr₆, (CH₃NH₃)₂SnBr_(6-y)I_(y),(CH₃NH₃)₂SnCl_(6-y)I_(y), (CH₃NH₃)₂SnCl_(6-y)Br_(y),(H₂N—C(H)═NH₂)₂SnI₆, (H₂N—C(H)═NH₂)₂SnBr₆,(H₂N—C(H)═NH₂)₂SnBr_(6-y)I_(y), (H₂N—C(H)═NH₂)₂SnCl_(6-y)I_(y) or(H₂N—C(H)═NH₂)₂SnCl_(6-y)Br_(y) wherein y is from 0.01 to 5.99. y may beas defined herein. For example, the hexahalometallate compound may be(CH₃NH₃)₂SnI₆, (CH₃NH₃)₂SnBr₆, (CH₃NH₃)₂SnCl₆, (H₂N—C(H)═NH₂)₂SnI₆,(H₂N—C(H)═NH₂)₂SnBr₆ or (H₂N—C(H)═NH₂)₂SnCl₆. The hexahalometallatecompound may be Cs₂SnI₆, Cs₂SnBr₆, Cs₂SnCl_(6-y)Br_(y), (CH₃NH₃)₂SnI₆,(CH₃NH₃)₂SnBr₆, or (H₂N—C(H)NH₂)₂SnI₆.

Conditions

In the processes of the invention, the second chamber is not under ahigh vacuum (i.e. the pressure in the second chamber is not less than10⁻⁴ mbar). The pressure in the second chamber is therefore greater than10′ mbar, for instance, the pressure of the second chamber may begreater than or equal to 1 mbar. The pressure in the second chambermeans that step (ii) is not typically a vacuum deposition.

In one embodiment, the pressure in the second chamber may be greaterthan or equal to 100 mbar. Preferably, the pressure in the secondchamber is greater than or equal to 500 mbar. The second chamber isoften at atmospheric pressure. Thus, the pressure in the second chambermay be from 900 mbar to 1100 mbar, for instance from 950 mbar to 1050mbar.

In a further embodiment, the pressure in the second chamber is abovehigh vacuum and is also less than atmospheric pressure. The pressure inthe second chamber may therefore be less than 1000 mbar. Consequently,the pressure in the second chamber is greater than 10⁻⁴mbar and may beless than 1000 mbar.

The second chamber comprises a vapour comprising the second precursorcompound during the production of the layer of the crystalline compound.The second chamber may comprise a carrier case, for instance an inertgas such as nitrogen, air, helium, neon, argon or krypton. The secondchamber often contains nitrogen or air.

The pressure in the first chamber is typically less than or equal to10⁻² mbar. Often, the pressure in the first chamber is less than orequal to 10⁻³ mbar. The pressure in the first chamber is therefore oftenat least a rough vacuum. Preferably, the pressure in the first chamberis less than or equal to 10⁻⁴ mbar. For instance, the pressure in thefirst chamber may be less than or equal to 10⁻⁵ mbar. Therefore, thefirst chamber is preferably under a high vacuum.

The pressure in the second chamber is higher than the pressure in thefirst chamber. For instance, the pressure in the first chamber may beless than or equal to 10⁻³mbar and the pressure in the second chamber isgreater than or equal to 100 mbar.

If the first chamber is under a high vacuum (for instance, less than orequal to 10⁻⁴ mbar) or, for instance, a pressure of less than or equalto 10⁻³ mbar, step (i) typically comprises vacuum deposition of thefirst precursor compound. As the pressure in the second chamber is abovehigh vacuum (for instance greater than 10⁻⁴ mbar or greater than orequal to 1 mbar), step (ii) typically comprises exposing the layer ofthe first precursor compound to a vapour comprising the second precursorcompound at a pressure of greater than 10⁻⁴ mbar (e.g. greater than orequal to 1 mbar).

Thus, in a first embodiment the process of the invention may comprise:

-   -   (i) producing a layer of a first precursor compound on a        substrate by vacuum deposition with a vapour comprising the        first precursor compound; and    -   (ii) exposing the layer of the first precursor compound to a        vapour of the second precursor compound at a pressure of greater        than or equal to 1 mbar, for instance greater than or equal to        500 mbar.

In a second embodiment the process of the invention may comprise:

-   -   (i) exposing a substrate to a vapour comprising a first        precursor compound in a first chamber to produce a layer of the        first precursor compound on the substrate, wherein the first        chamber is under a high vacuum; and    -   (ii) exposing the layer of the first precursor compound to a        vapour comprising a second precursor compound in a second        chamber to produce the layer of a crystalline material, wherein        the second chamber is not under a high vacuum.

In both processes, the vapour comprising the first precursor compound istypically produced by heating a composition comprising (or consistingessentially of) the first precursor compound. The composition comprisingthe first precursor compound is typically heating in a vessel such as acrucible (which is the source of the vapour). The vapour produced byheating the first precursor compound travels to the substrate, which isoften placed above the heated composition, and condenses on thesubstrate to form a layer of the first precursor compound. Thecomposition comprising, or consisting essentially of, the firstprecursor compound is typically heated at a temperature of from 50° C.to 250° C., for instance from 50° C. to 150° C. or from 150° C. to 250°C. The substrate is usually placed from 1 cm to 20 cm (for instance form5 cm to 10 cm) away from the source of the vapour of the first precursorcompound.

The rate of disposition of the first precursor compound is often from0.05 to 1.0 nm/s, for instance from 0.1 to 0.5 nm/s. The substrate isoften exposed to the vapour comprising the first precursor compound forfrom 1 minute to 1 hour, for instance from 10 minutes to 30 minutes.

Step (i) is continued until a layer of the first precursor compound ofdesired thickness is formed on the substrate. For instance, thesubstrate may be exposed to the vapour comprising the first precursorcompound until a layer of the first precursor compound having athickness of from 10 nm to 1 μm, for instance from 100 nm to 500 nm isformed. Often, the layer of the first precursor compound has a thicknessof greater than or equal to 100 nm. Preferably, exposure is continueduntil a layer having a thickness of from 200 nm to 300 nm is formed.

Step (ii) comprises exposing the layer of the first precursor compoundto a vapour comprising a second precursor compound in a second chamberto produce the layer of a crystalline material, wherein the secondchamber is not under a high vacuum, step (ii) is not a vacuum depositionprocess. Step (ii) may comprise: annealing (i.e. heating) the layer ofthe first precursor compound on the substrate in an atmospherecomprising a vapour comprising a second precursor compound to producethe layer of a crystalline material.

Typically, the second chamber is a sealed chamber comprising: thesubstrate with the layer of the first precursor compound disposedthereon; a solid composition comprising, or consisting essentially ofthe second precursor compound; the vapour comprising the secondprecursor compound; and optionally a carrier gas, for instance air ornitrogen. The second chamber may further comprise a solvent such thatthe solvent annealing step described below occurs simultaneously withstep (ii).

The process typically further comprises producing the vapour comprisinga second precursor compound by heating the second precursor compound inthe second chamber. The second chamber may be a sealed chambercomprising the layer of the first precursor compound on a substrate anda solid composition comprising, or consisting essentially of, the secondprecursor compound. The solid composition comprising, or consistingessentially of, the second precursor compound may be placed in acrucible which is heated, or it may be placed directly on an interiorsurface of the second chamber, for instance on the floor of the secondchamber, and the second chamber may then be heated. The second chambermay be placed on a hot plate. Upon heating the second chamber, thesecond precursor compound may sublime to form a vapour comprising thesecond precursor compound which fills the second chamber. The layer ofthe first precursor compound is then exposed to the vapour comprisingthe second precursor compound (for instance as an atmosphere of thevapour) which allows the formation of the layer of the crystallinematerial.

The layer of the first precursor compound is typically exposed to avapour comprising the second precursor compound in the second chamber toproduce the layer of a crystalline material for from 10 minutes to 12hours or from 30 minutes to 6 hours. The layer of the first precursorcompound is exposed to a vapour comprising a second precursor compoundfor a time sufficient to allow formation of the layer of the crystallinematerial. The layer of the first precursor compound is typically exposedto a vapour comprising a second precursor compound for from 1 to 4hours, for instance from 1.5 to 2.5 hours.

Typically, the first chamber and the second chamber are differentchambers, i.e. they are unconnected chambers. The substrate comprisingthe layer of the first precursor compound is therefore often transportedfrom the first chamber to the second chamber following step (i). Thesubstrate comprising the layer of the first precursor compound istherefore often transported through air to the second chamber.

Thus, a typical process according to the invention may comprise:

-   -   (a) placing a substrate within a first chamber comprising a        composition comprising, or consisting essentially of, the first        precursor compound and evacuating the first chamber such that        the pressure is less than or equal to 10⁻⁴ mbar (or another        pressure as described herein for the first chamber);    -   (b) heating the composition comprising, or consisting        essentially of, the first precursor compound to produce a vapour        comprising the first precursor compound and exposing the        substrate to the vapour comprising the first precursor compound        in the first chamber to produce a layer of the first precursor        compound on the substrate;    -   (c) transferring the layer of the first precursor compound on        the substrate from the first chamber to a second chamber (or        allowing it to be transferred) at greater than 10⁻⁴ mbar (for        instance at greater than or equal to 1 mbar, for instance at        greater than or equal to 500 mbar or at atmospheric pressure)        which comprises a composition comprising, or consisting        essentially of, a second precursor compound;    -   (d) heating the composition comprising, or consisting        essentially of, the second precursor compound to produce a        vapour comprising the second precursor compound at a pressure of        greater than 10⁻⁴ mbar (for instance at greater than or equal to        1 mbar, for instance at greater than or equal to 500 mbar or at        atmospheric pressure); and    -   (e) exposing the layer of the first precursor compound to the        vapour comprising the second precursor compound (e.g. an        atmosphere of the vapour) in a second chamber (optionally for a        time of from 30 minutes to 6 hours) to produce the layer of a        crystalline material, wherein the pressure in the second chamber        is greater than 10⁻⁴ mbar (or at greater than or equal to 1        mbar, for instance at greater than or equal to 500 mbar or at        atmospheric pressure).

In some embodiments, the first chamber and the second chamber are thesame chamber. Thus, there is one chamber which is referred to as thefirst chamber during step (i) and which is then referred to as thesecond chamber during step (ii). In such an arrangement, the pressure inthe single chamber is typically increased between step (i) and step(ii). For instance, the chamber may be evacuated (to lower the pressure)to act as the first chamber for step (i), before a carrier gas or thevapour comprising the second precursor compound is introduced into thechamber to increase the pressure such that the chamber acts as thesecond chamber during step (ii).

Often, step (i) comprises vacuum deposition of the first compound (forinstance in a first chamber at a pressure of less than or equal to 10⁻⁴mbar) and step (ii) comprises annealing or heating the layer of thefirst precursor compound in vapour comprising the second precursorcompound at a pressure of greater than 10⁻⁴ mbar (for instance greaterthan or equal to 1 mbar). Vacuum deposition is typically a directionaldeposition whereby molecules of the compound being deposited travel in astraight or substantially straight line to the substrate. Thus vacuumdeposition requires a low pressure to prevent collision of the moleculesof the compound being disposed with other molecules or particles in theatmosphere. In contrast, step (ii) comprises exposing the layer of thefirst precursor compound to a vapour comprising a second precursorcompound in a second chamber to produce the layer of a crystallinematerial, wherein the pressure in the second chamber is greater than10⁻⁴ mbar (for instance greater than or equal to 1 mbar). High vacuum isconsidered to be where the mean free path of a gas or vapour is longerthan the size of the chamber, such that there are very few collisionsbetween molecules or particles in the vapour/gas (i.e. molecular flow).At pressures above high vacuum (e.g. at greater than or equal to 1 mbar)molecules of the second precursor compound typically collide frequentlywith other gaseous molecules or particles in the second chamber. Thelayer of the first precursor compound is therefore exposed to anon-directional vapour comprising the second precursor compound. This isthought to improve formation of the layer of the crystalline material.

The crystalline material is formed by reaction between the layer of thefirst precursor compound and vapour comprising the second precursorcompound.

Typically, the mean free path of the vapour of the first precursorcompound is greater than or equal to 10 nun or the mean free path of thevapour of the second precursor compound is less than or equal to 0.1 mm.For instance, the mean free path of the vapour of the first precursorcompound may be greater than or equal to 10 mm and the mean free path ofthe vapour of the second precursor compound may be less than or equal to0.1 mm. Often, the mean free path of the vapour of the first precursorcompound is greater than or equal to 100 mm or the mean free path of thevapour of the second precursor compound is less than or equal to 1 μm.The mean free path of a vapour may be calculated based on, for instance,temperature and pressure.

The temperature of the second chamber is often greater than or equal to50° C. or greater than or equal to 100° C. The temperature is typicallysufficient to allow some of the second precursor compound to sublime.For instance, temperature of the second chamber may be from 100° C. to500° C. Preferably, the temperature of the second chamber may be from100° C. to 250° C. The temperature of the walls of the second chamber istypically greater than the temperature of the substrate, as this canprevent deposition of the second precursor compound on the walls of thesecond chamber. In some cases, the temperature of the second chamber isless than or equal to 150° C.

Precursor Compounds

The first and second precursor compounds may be any suitable precursorcompounds for formation of the crystalline material. Additionalprecursor compounds may be present in either step (i) or step (ii).

Typically (i) the first precursor compound comprises one or more firstcations and one or more first anions and (ii) the second precursorcompound comprises one or more second cations and one or more secondanions.

The one or more first cations are typically selected from metal cations.Metal cations include any cation of metals in groups 1 to 14 of theperiodic table. The one or more first cations are often one or moremetal monocations, one or more metal dications, or one or more metaltetracations. Preferably, the one or more first cations are one or moremetal dications or one or more metal tetracations. Often, the one ormore first cations are a single type of metal cation, for instance asingle metal dication or a single metal tetracation. If the crystallinematerial comprises a perovskite, the one or more first cations typicallycomprise one or more metal dications. If the crystalline materialcomprises a hexahalometallate, the one or more first cations typicallycomprise one or more metal tetracations.

The one or more first anions are typically selected from halide anionsand chalcogenide anions. The one or more first anions are often selectedfrom halide anions. The one or more first anions are often a single typeof halide anion.

The one or more second cations are typically selected from metalcations, ammonium and organic cations. The one or more second cationsare typically one or more monocations.

The one or more second anions are typically selected from halide anionsand chalcogenide anions. The one or more second anions are oftenselected from halide anions. The one or more second anions are often asingle type of halide anion.

Typically (i) the first precursor compound comprises a metal cation andone or more first anions and (ii) the second precursor compoundcomprises an inorganic cation (e.g. a caesium cation (Cs⁺), an ammoniumcation (NH⁴⁺) or an organic cation and one or more second anions.

Typically, the metal cation is Ca²⁺, Sr²⁺, Cd²⁺, Cu²⁺, Ni²⁺, Mn²⁺, Fe²⁺,Co²⁺, Pd²⁺, Ge²⁺, Sn²⁺, Pb²⁺, Yb²⁺, Eu²⁺, Pd⁴⁺, W⁴⁺, Re⁴⁺, Os⁴⁺, Ir⁴⁺,Pt⁴⁺, Sn⁴⁺, Pb⁴⁺, Ge⁴⁺, or Te⁴⁺; the one or more first anions areselected from halide anions; the inorganic cation is a caesium cation ora rubidium cation; the organic cation is an organic ammonium cation oran organic formamidinium cation; and the one or more second anions areselected from halide anions.

The organic cation may be any organic cation as described above. Forinstance, the organic cation may be selected from (NR¹R²R³R⁴)⁺,(R¹R²N═CR³R⁴)⁺, (R¹R²N—C(R⁵)═NR³R⁴)⁺ and (R¹R²N—C(NR⁵R⁶)═NR³R⁴)⁺,wherein each of R¹, R², R³, R⁴, R⁵ and R⁶ is independently H, asubstituted or unsubstituted C₁₋₂₀ alkyl group or a substituted orunsubstituted aryl group. R¹, R², R³, R⁴, R⁵ and R⁶ are typicallyindependently H, a substituted or unsubstituted C₁₋₆ alkyl group or asubstituted or unsubstituted aryl group. Preferably R¹, R², R³, R⁴, R⁵and R⁶ are independently H, or an unsubstituted C₁₋₆ alkyl group. Forinstance, R¹, R², R³, R⁴, R⁵ and R⁶ may independently be H, methyl,ethyl or propyl.

Preferably, the organic cation is selected from (R¹NH₃)⁺, (NR² ₄)⁺, and(H₂N—C(R¹)═NH₂)⁺, wherein R¹ is H, a substituted or unsubstituted C₁₋₂₀alkyl group or a substituted or unsubstituted aryl group, and each R² isindependently a substituted or unsubstituted C₁₋₁₀ alkyl group. Morepreferably, R¹ is H or an unsubstituted C₁₋₆ alkyl group and each R² isan unsubstituted C₁₋₆ alkyl group. For instance, R¹ may be H, methyl,ethyl or propyl and each R² may be methyl, ethyl and propyl. All R² maybe the same and may be methyl, ethyl and propyl. For instance, theorganic cation may be selected from (CH₃NH₃)⁺, (CH₃CH₂NH₃)⁺,(CH₃CH₂CH₂NH₃)⁺, (N(CH₃)₄)⁺, (N(CH₂CH₃)₄)⁺, (N(CH₂CH₂CH₃)₄)⁺,(H₂N—C(H)═NH₂)⁺ and (H₂N—C(CH₃)═NH₂)⁺.

Often, the metal cation is Cu²⁺, Ge²⁺, Sn²⁺, Pb²⁺; the one or more firstanions are selected from F⁻, Cl⁻, Br⁻ and I⁻; the organic cation is acation of formula (R⁵NH₃)⁺ wherein R⁵ is a unsubstituted or substitutedC₁₋₂₀ alkyl group or an unsubstituted or substituted aryl group; or theone or more second anions are selected from F⁻, Cl⁻, Br⁻ and I⁻. Forinstance, the metal cation may be Cu²⁺, Ge²⁺, Sn²⁺, Pb²⁺; the one ormore first anions may be selected from r, Cl⁻, Br⁻ and I⁻ the organiccation may be a cation of formula (R⁵NH³)⁺ wherein R⁵ is a unsubstitutedor substituted C₁₋₂₀ alkyl group or an unsubstituted or substituted arylgroup; and the one or more second anions may be selected from F⁻, Cl⁻,Br⁻ and I⁻.

If the metal cation is a dication, the crystalline material is often aperovskite, such as that described by formula (II) above. If the metalcation is a tetracation, the crystalline material is often ahexahalometallate as describe by formula (III) above.

If the crystalline material is a perovskite, the first precursorcompound is often a metal dihalide and the second precursor compound isoften a halide of an organic cation. If the crystalline material is ahexahalometallate, the first precursor compound is often a metaltetrahalide and the second precursor compound is often a halide of anorganic cation.

The first precursor compound may be a compound of formula BX₂ wherein Bis a metal cation and X is a halide anion; and/or the second precursorcompound may be a compound of formula AX′ wherein A is a monocation (forinstance an organic cation) and X′ is a halide anion. In some cases, Xand X′ are different halide anions. This is typically the case forperovskites.

The first precursor compound may, for instance, be selected from leaddifluoride, lead dichloride, lead dibromide, lead diiodide, tindifluoride, tin dichloride, tin dibromide, tin diiodide, copperdifluoride, copper dichloride, copper dibromide, copper diiodide,germanium difluoride, germanium dichloride, germanium dibromide,germanium diiodide, lead tetrafluoride, lead tetrachloride, leadtetrabromide, lead tetraiodide, tin tetrafluoride, tin tetrachloride,tin tetrabromide, tin tetraiodide, germanium tetrafluoride, germaniumtetrachloride, germanium tetrabromide, and germanium tetraiodide. Thefirst precursor compound may be selected from lead dichloride, leaddibromide, lead diiodide, tin dichloride, tin dibromide, tin diiodide,copper dichloride, copper dibromide, copper diiodide, germaniumdichloride, germanium dibromide, germanium diiodide, lead tetrachloride,lead tetrabromide, lead tetraiodide, tin tetrachloride, tintetrabromide, tin tetraiodide, germanium tetrachloride, germaniumtetrabromide, and germanium tetraiodide. Preferably, the first precursorcompound is selected from lead dichloride, lead dibromide, leaddiiodide, tin dichloride, tin dibromide, and tin diiodide.

The first precursor compound may be a compound of formula MX₄ wherein Mis a metal cation and X is a halide anion; and/or the second precursorcompound may be a compound of formula AX′ wherein A is said organiccation and X′ is a halide anion. In some cases, X and X′ are differenthalide anions. This is typically the case for hexahalometallates. Thefirst precursor compound may, for instance, be selected from leadtetrafluoride, lead tetrachloride, lead tetrabromide, lead tetraiodide,tin tetrafluoride, tin tetrachloride, tin tetrabromide and tintetraiodide.

The second precursor compound may, for instance, be selected from(H₃NR¹)X, (NR¹R²R³R⁴)X, (R¹R²N═CR³R⁴)X, (R¹R²N—C(R⁵)═NR³R⁴)X and(R¹R²N—C(NR⁵R⁶)═NR³R⁴)X, wherein each of R¹, R², R³, R⁴, R⁵ and R⁶ isindependently H, a substituted or unsubstituted C₁₋₂₀ alkyl group or asubstituted or unsubstituted aryl group, and X is F⁻, Cl⁻, Br⁻, or I⁻.Preferably the second precursor compound is (H₃NR¹)X, wherein R¹ is anunsubstituted C₁₋₆ alkyl group and X is Cl⁻, Br⁻, or I⁻.

The one or more second precursor compounds may, for example, be selectedfrom CsF, CsCl, CsBr, CsI, NH₄F, NH₄Cl, NH₄Br, NH₄I, (CH₃NH₃)F,(CH₃NH₃)Cl, (CH₃NH₃)Br, (CH₃NH₃)I, (CH₃CH₂NH₃)F, (CH₃CH₂NH₃)Cl,(CH₃CH₂NH₃)Br, (CH₃CH₂NH₃)I, (N(CH₃)₄)F, (N(CH₃)₄)Cl, (N(CH₃)₄)Br,(N(CH₃)₄)I, (H₂N—C(H)═NH₂)F, (H₂N—C(H)═NH₂)Cl, (H₂N—C(H)═NH₂)Br and(H₂N—C(H)═NH₂)I. Typically, the second precursor compounds is selectedfrom CsCl, CsBr, CsI, NH₄Cl, NH₄Br, NH₄I, (CH₃NH₃)Cl, (CH₃NH₃)Br,(CH₃NH₃)I, (CH₃CH₂NH₃)Cl, (CH₃CH₂NH₃)Br, (CH₃CH₂NH₃)I, (N(CH₃)₄)Cl,(N(CH₃)₄)Br, (N(CH₃)₄)I, (H₂N—C(H)═NH₂)Cl, (H₂N—C(H)═NH₂)Br and(H₂N—C(H)═NH₂)I.

Preferably, the first precursor compound is a lead dihalide, a tindihalide or a copper dihalide, for instance lead diiodide, tin diiodide,copper dibromide or copper dichloride, and the second precursor compoundis an alkylammonium halide, for instance methylammonium iodide,methylammonium bromide, or methylammonium chloride, or an ammoniumhalide, for instance ammonium iodide, ammonium bromide, or ammoniumchloride. The first precursor compound may be lead diiodide and thesecond precursor compound may be methylammonium iodide. The firstprecursor compound may be lead diiodide and the second precursorcompound may be methylammonium chloride. The first precursor compoundmay be tin diiodide and the second precursor compound may bemethylammonium iodide. The first precursor compound may be copperdibromide and the second precursor compound may be methylammoniumchloride. The first precursor compound may be copper dichloride and thesecond precursor compound may be methylammonium chloride. The firstprecursor compound may be copper dichloride and the second precursorcompound may be ammonium bromide.

Substrate

The substrate may be any suitable substrate. For instance, the substratemay be a substrate suitable for a semiconductor device.

The substrate typically comprises a layer of a first electrode material.Thus the substrate typically comprises one or more first electrodes. Thefirst electrode material may be any suitable electrically conductivematerial. Suitable conductive materials include metals, transparentconducting oxides, graphite, and conductive polymers. Examples of metalswhich may form the first electrode material include silver, gold,copper, aluminium, platinum, palladium, or tungsten. The first electrodematerial typically comprises, or consists essentially of, a transparentconducting oxide. The transparent conducting oxide may be selected fromfluorine doped tin oxide (FTO), indium tin oxide (ITO), or aluminiumzinc oxide (AZO), and preferably FTO. The first electrode material mayform a single layer or may be patterned.

The substrate typically comprises a layer of an n-type semiconductor ora layer of a p-type semiconductor. Preferably, the layer of an n-typesemiconductor or the layer of a p-type semiconductor is a compact layer.Compact layers are typically layers without open porosity. The thicknessof the layer of an n-type semiconductor or the layer of a p-typesemiconductor is typically from 10 nm to 500 nm. For instance, thethickness may be from 50 nm to 200 11M.

The n-type semiconductor may comprise an inorganic or an organic n-typesemiconductor. A suitable inorganic n-type semiconductor may be selectedfrom a metal oxide, a metal sulphide, a metal selenide, a metaltelluride, a perovskite, amorphous Si, an n-type group IV semiconductor,an n-type group III-V semiconductor, an n-type group II-VIsemiconductor, an n-type group I-VII semiconductor, an n-type groupIV-VI semiconductor, an n-type group V-VI semiconductor, and an n-typegroup II-V semiconductor, any of which may be doped or undoped.Typically, the n-type semiconductor is selected from a metal oxide, ametal sulphide, a metal selenide, and a metal telluride. Thus, then-type semiconductor may be an inorganic material selected from oxide oftitanium, tin, zinc, niobium, tantalum, tungsten, indium, gallium,neodymium, palladium, or cadmium, or an oxide of a mixture of two ormore of said metals. For instance, the n-type semiconductor may compriseTiO₂, SnO₂, ZnO, Nb₂O₅, Ta₂O₅, WO₃, W₂O₅, In₂O₃, Ga₂O₃, Nd₂O₃, PbO, orCdO. Preferably, the n-type semiconductor comprises, or consistsessentially of, TiO₂. The substrate may comprise a compact layer oftitanium dioxide.

The p-type semiconductor may comprise an inorganic or an organic p-typesemiconductor. Typically, the p-type semiconductor comprises an organicp-type semiconductor. Suitable ptype semiconductors may be selected frompolymeric or molecular hole transporters. The ptype semiconductor maycomprise spiro-OMeTAD (2,2′,7,7′-tetrakis-(N,N-di-pmethoxyphenylamine)9,9′-spirobifluorene)), P3HT (poly(3-hexylthiophene)), PCPDTBT(Poly[2,1,3-benzothiadiazole-4,7-diyl[4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2,6-diyl]])or PVK (poly(N-vinylcarbazole)). The p-type semiconductor may comprisecarbon nanotubes. Usually, the p-type semiconductor is selected fromspiro-OMeTAD, P3HT, PCPDTBT and PVK. Preferably, the p-typesemiconductor is spiro-OMeTAD.

The substrate may, for instance, comprise a layer of a first electrodematerial and a layer of an n-type semiconductor. Often, the substratecomprises a layer of a transparent conducting oxide, for instance FTO,and a compact layer of an n-type semiconductor, for instance TiO₂.

In some embodiments, the substrate comprises a layer of a porousscaffold material.

The layer of a porous scaffold is usually in contact with a layer of ann-type or p-type semiconductor material, for instance a compact layer ofan n-type semiconductor or a compact layer of a p-type semiconductor.The scaffold material is typically mesoporous or macroporous. Thescaffold material may aid charge transport from the crystalline materialto an adjacent region. The scaffold material may also aid formation ofthe layer of the crystalline material during deposition. The porousscaffold material is typically infiltrated by the crystalline materialafter deposition.

Typically, the porous scaffold material comprises a dielectric materialor a charge-transporting material. The scaffold material may be adielectric scaffold material. The scaffold material may be acharge-transporting scaffold material. The porous scaffold material maybe an electron-transporting material or a hole-transporting scaffoldmaterial. N-type semiconductors are examples of electron-transportingmaterials. p-type semiconductors are examples of hole-transportingscaffold materials. Preferably, the porous scaffold material is adielectric scaffold material or a electron-transporting scaffoldmaterial (e.g. an n-type scaffold material).

The porous scaffold material may be a charge-transporting scaffoldmaterial (e.g. an electrontransporting material such as titania, oralternatively a hole transporting material) or a dielectric material,such as alumina. The term “dielectric material”, as used herein, refersto material which is an electrical insulator or a very poor conductor ofelectric current. The term dielectric therefore excludes semiconductingmaterials such as titania. The term dielectric, as used herein,typically refers to materials having a band gap of equal to or greaterthan 4.0 eV. (The band gap of titania is about 3.2 eV.) The skilledperson of course is readily able to measure the band gap of a materialby using well-known procedures which do not require undueexperimentation. For instance, the band gap of a material can beestimated by constructing a photovoltaic diode or solar cell from thematerial and determining the photovoltaic action spectrum. Themonochromatic photon energy at which the photocurrent starts to begenerated by the diode can be taken as the band gap of the material;such a method was used by Barkhouse et al., Prog. Photovolt: Res. Appl.2012; 20:6-11. References herein to the band gap of a material mean theband gap as measured by this method, i.e. the band gap as determined byrecording the photovoltaic action spectrum of a photovoltaic diode orsolar cell constructed from the material and observing the monochromaticphoton energy at which significant photocurrent starts to be generated.

The thickness of the layer of the porous scaffold is typically from 5 nmto 300 nm. For instance, the thickness of the layer of the porousscaffold may be from 10 nm to 50 nm.

The substrate may, for instance, comprise a layer of a first electrodematerial, a layer of an ntype semiconductor, and a layer of a dielectricscaffold material. The substrate may therefore comprise a layer of atransparent conducting oxide, a compact layer of TiO₂ and a porous layerof Al₂O₃.

The thickness of the layer of the first precursor compound is typicallyfrom 50 nm to 1000 nm. Thus, the layer of the first precursor compoundmay be deposited until it has a thickness of from 50 nm to 1000 nm.Often, the layer of the first precursor compound has a thickness ofgreater than or equal to 100 nm.

The layer of the first precursor compound is often without openporosity. The layer of the crystalline compound is often without openporosity.

Solvent Annealing Step

In some cases it is desirable to perform an additional solvent annealingstep. The solvent annealing step can be used to obtain desired crystalsizes within the layer of the crystalline material. The solventannealing step can be performed simultaneously with step (ii) to improvecrystal formation. In the solvent annealing step the layer of thecrystalline material, or layer comprising the first precursor compoundand the crystalline material, is exposed to a solvent atmosphere andoptionally heated in this atmosphere.

Thus, the process may further comprise: (iii) exposing the layer of thecrystalline material to a vapour comprising a solvent.

The solvent annealing step may occur subsequently to step (ii) orsimultaneously with step (ii). If steps (iii) and (ii) occur at the sametime, the substrate comprising a layer of the first precursor compoundis exposed to a vapour comprising both the second precursor compound andthe solvent in a second chamber to produce the layer of a crystallinematerial.

The solvent may be any suitable solvent. The solvent may be a polarsolvent or a non-polar solvent. Typically the solvent is a polarsolvent. Examples of polar solvents include water, alcohol solvents(such as methanol, ethanol, n-propanol, isopropanol and n-butanol),ether solvents (such as dimethylether, diethylether andtetrahydrofuran), ester solvents (such as ethyl acetate), carboxylicacid solvents (such as formic acid and ethanoic acid), ketone solvents(such as acetone), amide solvents (such as dimethylformamide anddiethylformamide), amine solvents (such as triethylamine), nitrilesolvents (such as acetonitrile), sulfoxide solvents (dimethylsulfoxide)and halogenated solvents (such as dichloromethane, chloroform, andchlorobenzene). The solvent may be selected from polar protic solvents.Examples of protic polar solvents include water, methanol, ethanol,npropanol, isopropanol, n-butanol, formic acid, ethanoic acid. Examplesof non-polar solvents include alkanes (such as pentane and hexane),cycloalkanes (such as cyclopentane and cyclohexane), and arenes (such asbenzene, toluene and xylene).

The vapour comprising a solvent is usually produced by heating a sampleof the solvent. The solvent may be heated at a temperature of from 10°C. to 200° C. For instance, the solvent may be heated at a temperatureof from 50° C. to 150° C. The solvent annealing step may occur in thesame chamber as step (ii), or the layer of the crystalline material maybe transferred to another chamber before the solvent annealing step isperformed. Step (iii) is typically performed in a sealed chambercontaining the layer of the crystalline material and solvent.

The substrate is usually heated during the solvent annealing step. Thelayer of the crystalline material may be heated at a temperature of from30° C. to 300° C. For instance, the layer of the crystalline materialmay be heated at a temperature of from 50° C. to 150° C. The layer ofthe crystalline material may be heated (i.e. annealed in the solventatmosphere) for from 10 minutes to 24 hours. For instance, layer of thecrystalline material may be heated for from 30 minutes to 12 hours, orfrom 1 hours to 6 hours. The pressure in the chamber during step (iii)is typically greater than or equal to 500 mbar. Typically, the pressureis approximately atmospheric, for instance from 950 mbar to 1050 mbar.

The process may further comprise an annealing step, step (iv). Thus, theprocess may further comprise: (iv) heating the layer of the crystallinematerial to a temperature of from 50° C. to 250° C. This step may be inaddition to step (iii), or may occur instead of step (iii). Thus, theprocess of the invention may comprise: steps (i) and (ii); steps (i),(ii) and (iii); steps (i), (ii) and (iv); or steps (i), (ii), (iii) and(iv).

The layer of the crystalline material is typically heated at atemperature of from 50° C. to 200° C., for instance at from 100° C. to200° C. The layer of the crystalline material may be heated (in step(iv)) for from 10 minutes to 24 hours. For instance, layer of thecrystalline material may be heated for from 30 minutes to 12 hours, orfrom 1 hours to 6 hours. The pressure in the chamber during step (iv) istypically greater than or equal to 500 mbar.

Typically, the pressure is approximately atmospheric, for instance from950 mbar to 1050 mbar.

One Step Process

The invention also provides a one step process for producing a layer ofa crystalline material. Thus, the invention provides a process forproducing a layer of a crystalline material, which process comprisesexposing a layer of a first precursor compound on a substrate to avapour comprising a second precursor compound in a chamber to producethe layer of a crystalline material, wherein the pressure in the chamberis greater than 10⁻⁴ mbar (for instance greater than or equal to 1 mbar)and less than atmospheric pressure.

A pressure which is less than atmospheric pressure will depend on theatmospheric pressure of the area in which the process is performed. Lessthan atmospheric pressure is typically less than or equal to 99% ofatmospheric pressure. Often, less than atmospheric pressure is less thanor equal to 95% of atmospheric pressure or less than or equal to 95% ofatmospheric pressure. Less than atmospheric pressure may be less than orequal to 1000 mbar or less than or equal to 950 mbar. Thus, the pressurein the chamber may be greater than or equal to 10⁻⁴ mbar and less thanor equal to 950 mbar. The pressure in the chamber is typically from 500mbar to 900 mbar. For instance, the pressure in the chamber is typicallyfrom 500 mbar to 900 mbar.

The chamber in which the one-step process comprises a vapour comprisinga second precursor compound. The chamber may also comprise other gasesor vapours, for instance a carrier gas. Often, however, the chamber doesnot comprise nitrogen (or comprises a partial pressure of less than orequal to 100 mbar or less than equal to 1 mbar of nitrogen).Alternatively, or additionally, the chamber sometimes does not compriseoxygen (or comprises a partial pressure of less than or equal to 100mbar or less than equal to 1 mbar of oxygen).

The layer of a first precursor compound on a substrate may be obtainableby solution-processing the first precursor compound or obtainable byvacuum deposition of the first precursor compound.

The one-step process according to the invention may be as describedabove for the two-step process of the invention. In particular, theone-step process may be as defined above for step (ii) of the two-stepprocess. Thus, the first and second precursor compounds may be asdefined above. The chamber in the one step process may be as defined forthe second chamber above.

Layer

The invention also provides a layer of a crystalline material obtainableby a process according to the invention for producing a layer of acrystalline material.

The layer of a crystalline material may be as defined herein. Forinstance, the layer of a crystalline material may be a layer withoutopen porosity. The crystalline material may a perovskite of formula (II)or a hexahalometallate compound of formula (III).

Process for Producing a Semiconductor Device

The invention also a process for producing a semiconductor devicecomprising a layer of a crystalline material, which process comprisesproducing said layer of a crystalline material by a process according tothe invention.

The process typically further comprises disposing on the layer of acrystalline material a layer of a p-type semiconductor or a layer of an-type semiconductor. Often, the process typically comprises disposingon the layer of a crystalline material a layer of a p-typesemiconductor. The n-type or p-type semiconductor may be as definedherein. For instance, the p-type semiconductor may be an organic p-typesemiconductor. Suitable p-type semiconductors may be selected frompolymeric or molecular hole transporters. Preferably, the p-typesemiconductor is spiro-OMeTAD. The layer of a p-type semiconductor or alayer of a n-type semiconductor is typically disposed on the layer ofthe crystalline material by solution processing, for instance bydisposing a composition comprising a solvent and the n-type or ptypesemiconductor. The solvent may be selected from polar solvents, forinstance chlorobenzene or acetonitrile. The thickness of the layer ofthe p-type semiconductor or the layer of the n-type semiconductor istypically from 50 nm to 500 nm.

The process typically further comprises disposing on the layer of thep-type semiconductor or n-type semiconductor a layer of a secondelectrode material. The second electrode material may be as definedabove for the first electrode material. Typically, the second electrodematerial comprises, or consists essentially of, a metal. Examples ofmetals which the second electrode material may comprise, or consistessentially of, include silver, gold, copper, aluminium, platinum,palladium, or tungsten. The thickness of the layer of a second electrodematerial is typically from 5 nm to 100 nm.

Examples of semiconductor devices include a photovoltaic device, a solarcell, a photo detector, a photodiode, a photosensor, a chromogenicdevice, a transistor, a light-sensitive transistor, a phototransistor, asolid state triode, a battery, a battery electrode, a capacitor, asuper-capacitor, a light-emitting device, or a light-emitting diode.

The semiconductor device is typically an optoelectronic device. Examplesof optoelectronic devices include photovoltaic devices, photodiodes(including solar cells), phototransistors, photomultipliers,photoresistors, and light emitting devices. Preferably, thesemiconductor device is a photovoltaic device.

The invention also provides a semiconductor device obtainable by aprocess for producing a semiconductor device according to the invention.

A photovoltaic device according to the invention may comprise thefollowing layers in the following order:

-   -   I. a layer of a first electrode material as defined herein;    -   II. a layer of an n-type semiconductor as defined herein    -   III. optionally a layer of a porous scaffold material as defined        herein;    -   IV. a layer of a crystalline material as defined herein;    -   V. a layer of an p-type semiconductor as defined herein; and    -   VI. a layer of a second electrode material as defined herein.

A photovoltaic device according to the invention may comprise thefollowing layers in the following order:

-   -   I. a layer of a transparent conducting oxide, preferably FTO;    -   II. a compact layer of an n-type semiconductor as defined        herein, preferably TiO₂;    -   III. optionally a layer of a porous scaffold material as defined        herein, preferably Al₂O₃ or TiO₂;    -   IV. a layer of a crystalline material as defined herein;    -   V. a layer of an p-type semiconductor as defined herein,        preferably spiro-OMeTAD; and    -   VI. a layer of a second electrode material comprising gold or        silver.

The layer of the first electrode material may have a thickness of from100 nm to 700 nm, for instance of from 100 nm to 400 nm. The layer ofthe second electrode material may have a thickness of from 10 nm to 500nm, for instance from 50 nm to 200 nm or from 10 nm to 50 nm. The layerof an n-type semiconductor may have a thickness of from 50 nm to 500 nm.The layer of an p-type semiconductor may have a thickness of from 50 nmto 500 nm.

The invention will now be further described by the following Examples.

EXAMPLES Example 1

A photovoltaic device comprising a layer of a methylammonium lead iodideperovskite was produced by the following procedure which includes thetwo-step vapour/vapour deposition method according to the invention. FTOglass was first cleaned before being spin-coated with an electronselective layer of TiO₂ having a thickness of approximately 50 nm. Alayer of lead diiodide (PbI₂) was then evaporated onto the electronselective layer at a pressure of approximately 5×10-6 mbar and a rate of0.2 nm/s until a layer of PbI₂ having a thickness of from 250 to 300 nmwas formed. The sample comprising the PbI2 layer was then transferredthrough a lab atmosphere to a nitrogen filled glovebox. The sample wasput in a covered glass container at atmospheric pressure together withmethylammonium iodide (MAI, CH₃NH₃I) and the container was heated to150° C. The substrate and the MAI powder were held at the sametemperature for 2 hours. The PbI₂ layer was converted to methylammoniumlead iodide perovskite under exposure to the sublimed vapour of MAI. Thedevice was completed by spin-coating a layer of spiro-OMeTAD as a holetransport material and finally evaporating Au/Ag electrodes.

A scanning electron microscope (SEM) image of a top view of the layer ofthe methylammonium lead iodide perovskite produced by this two-stepdeposition method is shown in FIG. 1(A). Short and large scalecross-sections of the device incorporating the methylammonium leadiodide film grown by this two-step vapour deposition are shown in FIGS.1(B) and 1(C) respectively. FIGS. 1(B) and 1(C) show that the producedperovskite films have considerable uniformity of surface coverage andthickness.

Powder X-ray diffraction (XRD) patterns were taken before and after theconversion of the PbI₂ layer to the perovskite. These are shown in FIG.2 together with a control XRD pattern of the FTO+TiO₂ substrate. Peaksobserved in the FTO+TiO₂ substrate XRD are marked with a dash (-), peaksobserved in the PbI₂ XRD are marked with a plus (+) and peaks observedin the MAPbI₃ XRD are marked with an asterisk (*). These peaks show thatthe PbI₂ has been converted to MaPbI₃.

The device produced by the above method was characterised undersimulated AM1.5 sunlight. The current-voltage characteristics of thedevice are shown in FIG. 3. The device performance parameters measuredwere: J_(SC)=18.1 mA/cm²; V_(OC)=0.81 V; FF=0.62; power conversionefficiency (PCE)=9.24%; and intensity=0.986 suns. A significant PCE of9.24% was therefore observed by a device produced by a method using atwo-step vapour deposition method according to the invention. Aschematic diagram of the two-step vapour deposition process is shown inFIG. 4.

Example 2

Layers of lead iodide (PbI₂) were produced by either spin-coating asolution comprising PbI₂ (comparative) or by vacuum evaporating PbI₂ ata pressure of approximately 5×10-6 mbar (the invention). These layerswere then exposed to a sublimed vapour of methylammonium iodide (MAI) atapproximately atmospheric pressure for 90 minutes by placing the PbI₂layers in a heated sealed container with MAI powder. FIG. 5 shows SEMimages of top-views of the produced layers. FIG. 5(a) shows a top-viewSEM of a spin-coated PbI₂ surface. FIG. 5(b) shows a top-view SEM of amethylammonium lead triiodide surface produced by exposing thespin-coated PbI₂ surface of FIG. 5(a) to the vapour of MAI. FIG. 5(c)shows a top-view SEM of an evaporated PbI₂ surface. FIG. 5(d) shows atop-view SEM of a methylammonium lead triiodide surface produced byexposing the evaporated PbI₂ surface of FIG. 5(c) to the vapour of MAI.

The conversion of the spin-coated layer of PbI₂ to CH₃NH₃PbI₃ can beseen in FIG. 6 which shows a number of XRD patterns taken of the PbI₂film before exposure to the MAI vapour and after 30 minutes exposure, 60minutes exposure and 90 minutes exposure. After 90 minutes totalconversion of the layer to the perovskite methylammonium lead triiodideis observed. The conversion of the spin-coated layer of PbI₂ toCH₃NH₃PbI₃ can also be observed from FIG. 7 which shows the change inthe UV vis absorbance spectra of the methylammonium lead triiodide filmsproduced after exposure of the spin-coated PbI₂ to the MAI atmosphereafter 30, 60 or 90 minutes.

Photovoltaic devices were then constructed comprising methylammoniumlead triiodide films fabricated by organic vapour conversion ofspin-coated or evaporated PbI₂ films as described above. The deviceswere completed by spin-coating a solution comprising spiro-OMeTAD as ahole-transporter material and evaporating Au/Ag electrodes.Cross-sectional SEM images of the completed devices are shown in FIG. 8,with (a) showing the cross-section of a device containing a perovskitelayer produced from spin-coated PbI₂ and (b) showing the cross-sectionof a device containing a perovskite layer produced from evaporated PbI₂.In the SEM images the layers, from bottom to top, are: glass, FTO,compact TiO₂, MAPbI₃ perovskite, spiro-OMeTAD, Au/Ag electrode. Theseare planar heterojunction devices.

Comparative Example 1

A photovoltaic device comprising a methylammonium lead triiodideperovskite layer produced from the spin-coated layer of PbI₂ togetherwith a mesoporous layer of TiO₂ was also produced. The perovskite wasthen formed from the spin-coated layer of PbI₂ by exposure to asaturated atmosphere of MAI as in Examples 1 and 2. The structure ofthis device was the same as the planar heterojunction devices producedin Example 2 except the additional mesoporous layer was included betweenthe compact TiO₂ layer and the perovskite. The current-voltage devicecharacteristics of the planar heterojunction device containing theperovskite derived from spin-coated PbI₂ is shown in FIG. 9 (upper)together with the device comprising a methylammonium lead triiodideperovskite layer produced from the spin-coated layer of PbI₂ togetherwith a mesoporous layer of TiO2 (lower). Both devices were produced byspin coating layers of PbI₂. The device parameters of the planarheterojunction device (upper figure) are: J_(SC)=16.9 mA/cm²;V_(OC)=0.88 V; FF=0.54; and PCE=7.69%. The device parameters of themesoporous TiO₂ device (lower figure) are: J_(SC)=16.4 mA/cm²;V_(OC)=0.76 V; FF=0.51; and PCE=6.17%. It can therefore be seen that thevapour-vapour two-step process of Example 1 produces devices whichoutperform (PCE of 9.24%) those produced by a solution-vapour two-stepprocess (FIG. 9, Comparative Example 1, PCEs of less than 7.7%).

Example 3

A two-step process was used to produce other perovskite materials.Methylammonium tin iodide was produced by converting a spin-coated layerof tin iodide in a methylammonium iodide (MAI) atmosphere. The partialconversion of the layer of SnI₂ to CH₃NH₃SnI₃ is shown in FIG. 10 whichshows the XRD patter of SnI2 alone and after 15 exposure to an MAIatmosphere. Perovskite peaks are marked with a *.

FIGS. 11, 12 and 13 show XRD patterns of copper based materials producedusing a spin-coated metal halide/vapour deposited organic method.Exposure to the atmosphere of the nitrogen containing component was forapproximately 90 minutes. FIG. 11 shows the XRD of a perovskite producedby exposing a spin-coated layer of CuBr₂ to an atmosphere ofmethylammonium chloride. FIG. 12 shows the XRD of a perovskite producedby exposing a spin-coated layer of CuCl₂ to an atmosphere ofmethylammonium chloride. FIG. 13 shows the XRD of a perovskite producedby exposing a spin-coated layer of CuCl₂ to an atmosphere of ammoniumchloride (NH₄Cl). The UV-vis absorption spectra of the first two ofthese materials (CuBr₂+methylammonium chloride and CuCl₂+methylammoniumchloride) are shown in FIG. 14.

Comparative Example 2

In order to provide a comparison with a vacuum/solution based method,the following experiment was performed. A thin TiO₂ electron-selectivelayer was spin-coated from a mildly acidic precursor solution oftitanium isopropoxide in anhydrous ethanol onto clean FTO-coated glassand annealed for 30 minutes at 500° C. This was then transferred to avacuum evaporation chamber and a 250 nm thin-film of either PbI₂ orPbCl₂ was evaporated at a pressure of ˜5×10⁻⁶ mbar. The substrates arethen dipped into a solution of methylammonium iodide (MAI) in anhydrousisopropanol for a prescribed time. The reaction rate was thermallycontrolled by placing the reaction vessel on a hotplate. During thisstep MAI intercalates into the lead halide lattice to form theperovskite. When the reaction was complete, the sample was rinsed inisopropanol and dried. For devices, a solution of spiro-OMeTAD inchlorobenzene containing Li-TFSI and tert-butyl pyridine was spin-coatedonto the perovskite layer as the hole-selective contact. The deviceswere completed following thermal evaporation of silver top contacts invacuum.

SEM images showing the evolution of perovskite crystal growth at roomtemperature by dip coating a PbCl₂ thin-film into a 20 mg/ml isopropanolsolution of methylammonium iodide after (a) 0 s, (b) 1 s, (c) 10 s, (d)100 s, (e) 1000 s, (f) 10000 s are shown in FIG. 15. The growth modeleads to random protrusions of plate-like and needle-like perovskitecrystals from the surface providing high-levels of roughness. FIG. 16then shows the normalised XRD spectra for films at different dippingtimes, t. The spectra indicate that perovskite formation occursimmediately upon dip coating the film, PbCl₂ is consumed as the dippingtime increases, and the reaction is almost complete after 10000 s. Thiscorresponds with a very rough film as shown in FIG. 15(f).

SEM images showing the evolution of perovskite crystal growth at roomtemperature by dip coating a PbI₂ thin-film into a 20 mg/ml isopropanolsolution of methylammonium iodide after (a) 0 s, (b) 1 s, (c) 10 s, (d)100 s, (e) 1000 s, (f) 8000 s are shown in FIG. 17. The growth mode alsoleads to random protrusions of plate-like and needle-like perovskitecrystals from the surface providing high-levels of roughness. FIG. 18then shows the normalised XRD spectra for films at different dippingtimes, t. The spectra indicate that perovskite formation occursimmediately upon dip coating the film, PbI2 is consumed as the dippingtime increases, and the reaction is complete at some point between1000-10000 s. This corresponds with a very rough film as shown in FIG.17(f).

Variation in the concentration of the MAI solution was alsoinvestigated. FIG. 19 shows morphology variation when forming perovskitefrom PbCl₂ at 90° C. after 500 seconds using the following MAIconcentraions: (a) 3 mg/ml, (b) 4 mg/ml, (c) 5 mg/ml, (d) 6 mg/ml, (e) 7mg/ml. FIG. 20 shows morphology variation when forming perovskite fromPbI2 at 90° C. after 500 seconds using the following MAI concentraions:(a) 3 mg/ml, (b) 4 mg/ml, (c) 5 mg/ml, (d) 6 mg/ml, (e) 7 mg/ml.

The current density-voltage characteristics from devices based on anactive layer formed by dip coating of a PbCl₂ film at 90° C. in asolution of 6.5 mg/ml MAI in isopropanol for 400 s as described aboveare shown in FIGS. 21, 22 and 23. The device structure is a planarheterojunction with TiO₂ coated onto the FTO-coated glass substrate asthe electron-selective contact, and silver on spiro-OMeTAD deposited ontop of the perovskite layer as the hole-selective contact. FIG. 21 showsthe J-V characteristics of the highest efficiency device(efficiency=P_(max)/P_(in)). This curve shows significant instability(J_(sc) is lower than J at maximum power output) suggesting that maximumpower extracted based on the curve will be unstable. FIG. 22 shows ahistogram of device efficiencies from 12 devices fabricated in the samebatch suggesting that devices fabricated with this procedure have a highfailure rate. FIG. 23 shows a histogram of J-V curve stability based onthe ratio of the expected power output of the device based on thefundamental J-V parameters to the maximum power output, P_(max)=J*Vevaluated at V where

$\frac{d\; P}{d\; V} = 0.$This suggests that unstable device characteristics are obtained for asignificant proportion of devices following the vapour/solutiontechnique,

Example 4

A two-step process was used to produce further perovskite materials.Formamidinium lead triiodide was produced by converting a layer of leadiodide of approximately 160 nm thickness by exposure to anon-directional vapour of formamindinium iodide (FAI) at approximately 1mbar for 120 minutes at 170° C. by placing the PbI₂ layer in a heatedchamber with FAI powder.

FIG. 24 shows a top-view SEM of the surface of the formamidinium leadtriiodide produced. The formation of FAPbI₃ can be seen by comparisonwith FIG. 2, which shows the XRD pattern of evaporated PbI₂, with FIG.25 which shows a XRD pattern taken of the film after exposure of thePbI₂ layer to the FAI vapour. The formation of FAPbI₃ can also beobserved from FIG. 26 which shows the UV-vis absorbance spectra of theformamidinium lead triiodide films produced after exposure of the PbI₂to the FAI vapour.

In order to provide a comparison with a vacuum based methods atatmospheric pressure, an attempt to produce a layer of formamidiniumlead triiodide by was performed. However, at atmospheric pressure therewas insufficient FAI vapour pressure to drive the conversion of the PbI₂layer. In order to overcome this lack of vapour pressure, thetemperature of the conversion chamber was increased, which lead todecomposition/degradation of the layer resulting in unsuccessfulformation of any formamidinium lead triiodide.

The invention claimed is:
 1. A process for producing a layer of acrystalline material comprising a perovskite or a hexahalometallate,which process comprises: (i) a physical vapour deposition stepcomprising exposing a substrate to a vapour comprising a first precursorcompound in a first chamber to produce a layer of the first precursorcompound on the substrate; and (ii) a chemical vapour deposition stepcomprising exposing the layer of the first precursor compound to avapour comprising a second precursor compound in a second chamber toproduce the layer of a crystalline material, wherein: the pressure inthe first chamber is less than or equal to 10⁻³ mbar; the pressure inthe second chamber is greater than or equal to 1 mbar; the firstprecursor compound comprises one or more first cations and one or morefirst anions; and the second precursor compound comprises one or moreorganic cations and one or more second anions.
 2. A process according toclaim 1, wherein in step (i) the substrate is exposed to a directionalvapour comprising the first precursor compound.
 3. A process accordingto claim 1, wherein in step (ii) the layer of the first precursorcompound is exposed to a non-directional vapour comprising the secondprecursor compound.
 4. A process according to claim 1, wherein thecrystalline material consists essentially of a perovskite or ahexahalometallate.
 5. A process according to claim 1, wherein thecrystalline material comprises a perovskite of formula (II):[A][B][X]₃  (II) wherein: [A] is at least one organic monocation; [B] isat least one metal cation, wherein [B] comprises at least one selectedfrom Ca²⁺, Sr²⁺, Cd²⁺,Cu²⁺, Ni²⁺, Mn²⁺, Fe²⁺, Co²⁺, Pd²⁺, Ge²⁺, Sn²⁺,Pb²⁺, Yb²⁺ and Eu²⁺; and [X] is at least one halide anion.
 6. A processaccording to claim 5, wherein [A] comprises one or more organic cationsselected from (CH₃NH₃)⁺, (CH₃CH₂NH₃)⁺, (CH₃CH₂CH₂NH₃)⁺, (N(CH₃)₄)⁺,(H₂N—C(H)═NH₂)⁺ and (H₂N—C(CH₃)═NH₂)⁺.
 7. A process according to claim5, wherein [A] comprises one or more cations selected from (CH₃NH₃)⁺,(H₂N—C(H)═NH₂)⁺ and Cs⁺.
 8. A process according to claim 1, wherein thecrystalline material comprises a hexahalometallate of formula (III):[A]₂[B][X]₆  (III) wherein: [A] is at least one organic monocation; [M]is at least one metal or metalloid tetracation; and [X] is at least onehalide anion.
 9. A process according to claim 1, wherein the pressure inthe first chamber is less than or equal to 10⁻³ mbar.
 10. A processaccording to claim 1, wherein the first chamber and the second chamberare the same chamber or different chambers.
 11. A process according toclaim 1, wherein the mean free path of the vapour of the first precursorcompound is greater than or equal to 10 mm or the mean free path of thevapour of the second precursor compound is less than or equal to 0.1 mm.12. A process according to claim 1, wherein the temperature of thesecond chamber is greater than or equal to 100° C.
 13. A processaccording to claim 1, wherein (i) the first precursor compound comprisesa metal cation and one or more first anions and (ii) the secondprecursor compound comprises an organic monocation and one or moresecond anions.
 14. A process according claim 13, wherein the metalcation is selected from Ca²⁺, Sr²⁺, Cd²⁺, Cu²⁺, Ni²⁺, Mn²⁺, Fe²⁺, Co²⁺,Pd²⁺, Ge²⁺, Sn²⁺, Pb²⁺, Yb²⁺, Eu²⁺, Pd⁴⁺, W⁴⁺, Re⁴⁺, Os⁴⁺, Ir⁴⁺, Pt⁴⁺,Sn⁴⁺, Pb⁴⁺, Ge⁴⁺, and Te⁴⁺; the one or more first anions are selectedfrom halide anions; the organic monocation is selected from an organicammonium cation and an organic formamidinium cation, or a caesiumcation; and the one or more second anions is a halide anion.
 15. Aprocess according to claim 14, wherein: the metal cation is selectedfrom Cu²⁺, Ge²⁺, Sn²⁺, Pb²⁺; the one or more first anions are selectedfrom F⁻, Cl⁻, Br⁻, and I⁻; the monocation is selected from organiccations of formula (R⁵NH₃)⁺wherein R⁵ is a unsubstituted or substitutedC₁₋₂₀ alkyl group or an unsubstituted or substituted aryl group; or theone or more second anions are selected from F⁻, Cl⁻, Br⁻, and I⁻.
 16. Aprocess according to claim 13, wherein: the first precursor compound isa compound of formula BX₂ wherein B is said metal cation and X is ahalide anion; or the second precursor compound is a compound of formulaAX′ wherein A is said organic monocation and X′ is a halide anion.
 17. Aprocess according to claim 1, wherein the first precursor compound is alead dihalide, a tin dihalide or a copper dihalide, and the secondprecursor compound is an alkylammonium halide, a formamidinium halide ora caesium halide.
 18. A process according to claim 1, wherein thesubstrate comprises a layer of an n-type semiconductor or a layer of ap-type semiconductor.
 19. A process according to claim 1, wherein thesubstrate comprises a layer of a porous scaffold material.
 20. A processaccording to claim 1, wherein the thickness of the layer of the firstprecursor compound is from 50 nm to 1000 nm.
 21. A process according toclaim 1, which process further comprises: (iii) exposing the layer ofthe crystalline material to a vapour comprising a solvent.
 22. A processaccording to claim 1, which process further comprises: (iv) heating thelayer of the crystalline material to a temperature of from 50° C. to250° C.
 23. A process for producing a semiconductor device comprising alayer of a crystalline material, wherein the process comprises producingsaid layer of a crystalline material by a process comprising: (i) aphysical vapour deposition step comprising exposing a substrate to avapour comprising a first precursor compound in a first chamber toproduce a layer of the first precursor compound on the substrate; and(ii) a chemical vapour deposition step comprising exposing the layer ofthe first precursor compound to a vapour comprising a second precursorcompound in a second chamber to produce the layer of a crystallinematerial, wherein: the pressure in the first chamber is less than orequal to 10⁻³ mbar; the pressure in the second chamber is greater thanor equal to 1 mbar; the first precursor compound comprises one or morefirst cations and one or more first anions; and the second precursorcompound comprises one or more organic cations and one or more secondanions.
 24. A process according to claim 23, which process furthercomprises disposing on the layer of a crystalline material a layer of ap-type semiconductor or a layer of a n-type semiconductor.
 25. A processaccording to claim 24, which process further comprises disposing on thelayer of the p-type semiconductor or n-type semiconductor a layer of asecond electrode material.
 26. A process according to claim 23, whereinthe semiconductor device is an optoelectronic device.
 27. A processaccording to claim 1, wherein the pressure in the second chamber isgreater than or equal to 100 mbar.